Crystalline germanosilicate materials of new CIT-13 topology and methods of preparing the same

ABSTRACT

The present disclosure is directed to the use of novel crystalline germanosilicate compositions in affecting a range of organic transformations. In particular, the crystalline germanosilicate compositions are extra-large-pore compositions, designated CIT-13 possessing 10- and 14-membered rings.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 15/169,816, filed Jun. 1, 2016, which claims priority to U.S.Patent Application No. 62/169,310, filed Jun. 1, 2015, the contents ofeach of which are incorporated by reference herein in their entiretiesfor all purposes.

TECHNICAL FIELD

The present disclosure is directed to novel crystalline germanosilicatecompositions and methods of producing the same. In particular, thedisclosure describes extra-large-pore crystalline germanosilicatecompositions, designated CIT-13, possessing 10- and 14-membered rings.The disclosure also describes methods of preparing these crystallinecompositions using organic structure-directing agents (OSDAs), andmethods of using these crystalline compositions.

BACKGROUND

Zeolites play an important role as heterogeneous catalysts and are usedin a variety of industrial settings. Initially, these materials werelargely developed to support the petroleum industry in the quest tocreate more selective, robust catalysts for making gasoline and otherfuels. Currently, these solids have emerged as specialty materials, withproperties that are based upon structure and chemical composition ableto handle specific large-scale applications. A notable current exampleis their use in the selective catalytic reduction (SCR) system thatreduces nitrous oxide emissions from on-road combustion engines. Whilethere is a considerable effort that must go into bringing a new materialfrom the discovery phase into a commercially viable catalyst, thereremains room for discovery of new structures with the hope that onemight emerge as superior to the existing materials.

One goal toward finding new materials has been the hope thatincreasingly large pores that retain some catalytic properties in theirinterior surfaces can be capable of handling larger feed molecules inthe oil upgrade arena.

Hence, interest remains in the discovery of new crystalline phases foruse in these applications. The present work is aimed at addressing thedeficiencies in the art.

SUMMARY

This disclosure describes the results of studies with a series ofmonoquaternary and diquaternary OSDAs each with different aromatic ringsubstitutions. By investigating the phase selectivity and kineticbehavior of these OSDAs as a function of synthesis conditions, a newcrystalline germanosilicate phase was discovered. The latter has beentermed CIT-13, and has been shown to possess a three dimensionalframework having pores defined by 10- and 14-membered rings. It is thefirst known crystalline silicate with this architecture.

Some embodiments, then, provide for a crystalline germanosilicatecomposition comprising a three dimensional framework having poresdefined by 10- and 14-membered rings.

The crystalline microporous germanosilicate compositions may also, oralternatively, be described as exhibiting at least one of:

(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five ofthe characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2,18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2,26.01±0.2, and 26.68±0.2 degrees 2-θ;

(b) a powder X-ray diffraction (XRD) pattern substantially the same asshown in FIG. 1(B) or FIG. 1(C); or

(c) unit cell parameters substantially equal to the following:

Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V(Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)

The crystalline germanosilicate compositions have frameworks, whereinthe pore dimensions of the 10- and 14-membered rings are 6.2×4.5 Å and9.1×7.2 Å, respectively. Additionally, in some embodiments, theframework may have a density of 16.4 tetrahedral atoms (“T-atoms”) pernm³. In some cases, the crystalline germanosilicate have a ratio ofSi:Ge atoms in a range of from 2:1 to 16:1.

The crystalline germanosilicate compositions may be prepared using, andin some cases contain, at least one substituted benzyl-imidazoliumorganic structure-directing agent (OSDA). Exemplary such substitutedbenzyl-imidazolium organic structure-directing agents include thosehaving a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C₁₋₃ alkyl.

The disclosure also contemplates aqueous compositions comprising:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one substituted benzyl-imidazolium organicstructure-directing agent (OSDA) as described above and elsewhereherein; and

(e) a crystalline microporous germanosilicate CIT-13 composition. Withinthis specification, the nature of the sources of silicon and germaniumoxide and the nature of the mineralizing agent are also described.

The disclosure also contemplates methods for preparing suchgermanosilicate CIT-13 compositions, the methods comprisinghydrothermally treating an aqueous composition comprising:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one substituted benzyl-imidazolium organicstructure-directing agent (OSDA) having a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C₁₋₃ alkyl, under conditions effectiveto crystallize a crystalline microporous germanosilicate composition ofthe inventive topology and/or any of the characteristics associated withthis inventive material. Again, the sources of silicon and germaniumoxide and the nature of the mineralizing agent and operable conditionsare described herein.

Once isolated, the crystalline microporous germanosilicate solidproducts may be further treated, for example by

(a) heating at a temperature in a range of from about 250° C. to about450° C.; or

(b) contacting with ozone or other oxidizing agent at a temperature in arange of 25° C. to 200° C.;

for a time sufficient to form a dehydrated or an OSDA-depleted product.

In other embodiments, the isolated crystalline microporousgermanosilicate compositions may be further treated by:

(a) treating the dehydrated or OSDA-depleted product with an aqueousalkali, alkaline earth, transition metal, rare earth metal, ammonium oralkylammonium salt; and/or

(b) treating the dehydrated or OSDA-depleted product with at least onetype of transition metal or transition metal oxide.

In other embodiments, the isolated germanosilicate solid products arecalcined in air or under inert atmosphere conditions at a temperature ina range of from about 600° C. to about 1200° C., preferably about 800°C. to about 1000° C., for about 4-8 hours. Longer or shorter times mayalso be employed.

The inventive materials may be used in a host of catalysis applicationswhich are also described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, devices, and systems disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIGS. 1(A-C) shows several sets of powder XRD patterns for CIT-13: FIG.1(A) shows CIT-13 as made (upper) and calcined (lower); FIG. 1(B) showsreproducibility of patterns of products made from gels with Si/Ge=4;FIG. 1(C) compares experimentally and theoretically derived sample.

FIGS. 2(A-E) illustrate the comparison between the crystal structure ofCIT-13 and UTL. FIGS. 2(A-B) shows the CIT-13 pore system seen from (A)the 14MR-portal direction and (B) the 10MR-portal direction. FIGS.2(C-D) show the UTL pore system seen from (C) the 14MR-portal directionand (D) the 12MR-portal direction. - dashed circles indicate location ofgermanium oxides within the lattice. FIG. 2(E) shows alternativeschematic representations of the CIT-13 structure. FIGS. 2(F-G) show SEMmicrographs of as-prepared CIT-13 crystals from rotating and staticconvection ovens, respectively.

FIG. 3 shows several additional XRD profiles from selectedcrystallization conditions that give high-purity CIT-13germanosilicates. The 1^(st) (top) profile is from the referencecondition of 0.8 SiO₂:0.2 GeO₂ (Si/Ge=4):0.5 OSDA⁺OH⁻:0.5 HF:10 H₂O at160° C. without seeding. Each of the following (2^(nd) to 8th) profileshas a specified condition deviated from the reference condition

FIG. 4 illustrates a kinetic study of the effect of gel Si/Ge ratio onthe crystallization of CIT-13. Only the gel Si/Ge ratio was changed andthe other parameters were controlled to be the same as the referencecondition. Asterisks denote impurity peaks.

FIG. 5(A) shows an XRD profile and FIG. 5(B) shows an SEM micrographimage of the IM-12 germanosilicate sample of UTL framework synthesizedin a hydroxide medium and examined to compare with CIT-13 in this study.The Si/Ge ratio of this UTL sample determined using EDS was 4.5.

FIG. 6 illustrates a kinetic study of the effect of water levels in thegel on the crystallization of CIT-13. Only gel H₂O/(Si+Ge) ratio waschanged and the other parameters were controlled to be the same as thereference condition.

FIG. 7 illustrates a kinetic study of the effect of amount of OSDA inthe gel on the crystallization of CIT-13. Only gel (OSDA)^(|)OH⁻/(Si+Ge)ratio and HF/(Si+Ge) ratio were changed and the other parameters werecontrolled to be the same as the reference condition. Asterisks denotesimpurity peaks.

FIG. 8 illustrates a kinetic study of the effect of crystallizationtemperature on the crystallization of CIT-13. Only the crystallizationtemperature was changed and the other parameters were controlled to bethe same as the reference condition

FIG. 9 shows SEM micrographs of CIT-13 crystallized at differenttemperatures: (A) 140° C., (B) 150° C., (C) 160° C. and (D) 175° C.

FIG. 10 shows XRD profiles of crystallized germanosilicate samples withvarious gel Si/Ge ratios from OSDA 4. Asterisks (*) denote impuritypeaks. Here, the impurity phase was identified as MFI.

FIG. 11 shows XRD profiles of crystallized germanosilicate samples withvarious gel Si/Ge ratios from OSDA 5. Asterisks (*) denote impuritypeaks

FIG. 12(A) shows XRD profiles of crystallized germanosilicate sampleswith various gel Si/Ge ratios from OSDA 6. Asterisks (*) denote impuritypeaks. FIG. 12(B) shows the relationship between the gel Si/Ge ratio andthe product CIT-13/GE ratios, as characterized by EDS.

FIG. 13 illustrates the typical powder XRD profiles of the resultantCIT-13 crystals at several levels of gel Si/Ge ratios from (A) OSDA 2and (B) OSDA 6, with gel compositions x/(x+1) SiO₂:1/(x+1) GeO₂:0.5(OSDA)+OH-:0.5 HF:10 H₂O where x is the gel Si/Ge ratio. Asterisks (*)denote impurity peaks.

FIGS. 14(A-B) show FIG. 14(A) the ¹H-decoupled ¹³C Solid-State MAS (8k)NMR spectra (upper spectra) of OSDA 2 and OSDA 6 filling the pores andchannels of the as-prepared CIT-13 inorganic frameworks overlapped withthe corresponding ¹³C liquid NMR spectra (lower peaked spectra) of eachOSDA. FIG. 14(B) The TGA profiles of as-prepared CIT-13 synthesized fromOSDA 2 and OSDA 6.

FIGS. 15(A-B) show 87K Ar-cryogenic physisorption isotherms ofas-calcined CIT-13 and IM-12, FIG. 5(A) linear and FIG. 5(B) log scale.

FIG. 16(A) shows ²⁹Si 8K MAS solid-state NMR spectra of as-calcinedCIT-13 (lower trace) and IM-12 (upper trace). FIG. 16(B) shows thedeconvoluted ²⁹Si 8K MAS solid-state NMR spectra of as-calcined CIT-13(Si/Ge=5.0), with chemical shifts at −104.6 ppm (3.8%), −107.31 ppm(4.5%), −110.47 ppm (17.9%), −113.05 ppm (32.0%), −116.06 ppm (16.5%),−118.03 ppm (25.1%). Solid line is actual spectrum; dotted line is sumof the indicated peaks.

FIGS. 17(A-C) shows a comparison of differential pore size distributionfor IM-12 and CIT-13.

FIG. 18(A) shows powder XRD profiles of CIT-13 from HF-protocol andNH₄F-protocol. FIGS. 18(B-C) show SEM micrograph images of CIT-13 from(B) HF-protocol and (C) NH₄F-protocol. FIG. 18(D) provides TGA profilesof CIT-13 from HF-protocol and NH₄F-protocol. FIG. 18 (E) CryogenicArgon adsorption and desorption isotherms of CIT-13 from HF-protocol andNH₄F-protocol at 87 K.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention is directed to new compositions of matter,including those comprising crystalline microporous germanosilicates, andmethods of making and using these compositions

The present invention may be understood more readily by reference to thefollowing description taken in connection with the accompanying Figuresand Examples, all of which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific products,methods, conditions or parameters described or shown herein, and thatthe terminology used herein is for the purpose of describing particularembodiments by way of example only and is not intended to be limiting ofany claimed invention. Similarly, unless specifically otherwise stated,any description as to a possible mechanism or mode of action or reasonfor improvement is meant to be illustrative only, and the inventionherein is not to be constrained by the correctness or incorrectness ofany such suggested mechanism or mode of action or reason forimprovement. Throughout this text, it is recognized that thedescriptions refer to compositions and methods of making and using saidcompositions. That is, where the disclosure describes or claims afeature or embodiment associated with a composition or a method ofmaking or using a composition, it is appreciated that such a descriptionor claim is intended to extend these features or embodiment toembodiments in each of these contexts (i.e., compositions, methods ofmaking, and methods of using).

Compositions

The present invention is directed to a novel set of compositionsdescribed collectively as CIT-13. In some embodiments, the novelcompositions are described in terms of crystalline microporousgermanosilicate compositions comprising a three dimensional frameworkhaving pores defined by 10- and 14-membered rings. As should be apparentfrom the descriptions herein, these 10- and 14-membered rings comprisesilicon-oxygen and germanium-oxygen linkages. The 10- and 14 memberedrings are defined by convention as referring to the number ofalternating oxygen atoms in the respective rings and not the totalnumber of atoms. Additionally, this number of oxygen atoms in the ringalso equals the number of tetrahedral atoms in the ring.

In other embodiments, the crystalline microporous germanosilicatecompositions may be described in terms of those compositions thatexhibit at least one of characteristics:

(a) a powder X-ray powder diffraction (XRD) pattern exhibiting at leastfive of the characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2,18.26±0.2, 18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2,24.55±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ;

(b) a powder X-ray powder diffraction (XRD) pattern substantially thesame as shown in FIG. 1(A), 1(B) or 1(C); or

(c) unit cell parameters substantially equal to the following:

Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V(Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)The crystalline compositions may exhibit one, two, or all three of thecharacteristics described in (a), (b), or (c). In addition to thesefeatures, these crystalline microporous germanosilicates may also beseparately or additionally characterized and/or defined in any of theadsorption/desorption properties or ¹H, ¹³C, or ²⁹Si NMR data providedherein (for example, as provided at least in FIGS. 14-17).

It should be appreciated that these crystalline germanosilicates mayalso be characterized/defined in terms of any combination of structuraland physical data. Similarly, while it is believed that the structuresdescribed herein are true and accurate, the novelty of these newmaterials is not necessarily defined by the exactness of thedescriptions of these structures, should any future information beidentified that later causes a re-characterization of the structure.Similarly, as the physical data are may be effected by experimentalartifacts, the exactness of any specific data point may be subject tosuch experimental variability.

As described above, the crystalline microporous germanosilicatecompositions may be defined in terms of their powder X-ray diffraction(XRD) pattern, as exhibiting at least five of the characteristic peaksat 6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2, 18.36±0.2, 18.63±0.2,20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2, 26.01±0.2, and 26.68±0.2degrees 2-θ. In separate embodiment, the composition may exhibits six,seven, eight, nine, or ten of these characteristic peaks. Likewise, inother embodiment, the composition may exhibit 5, 6, 7, 8, 9, 10, or moreof the peaks identified in Table 3.

In other embodiments, the crystalline compositions exhibit a powderX-ray powder diffraction (XRD) pattern substantially the same as shownin FIG. 1(A), 1(B) or 1(C). Note here that the relative intensities ofthe peaks shown in these or any other figures, or identified in Table 3may be subject to experimental variations, for example due to scanningspeed, sample separation, particle size, degree if crystallinity (e.g.,related to degree of heat processing). For example, pre-calcinedmaterials isolated from the mixtures used to prepare them, may exhibitbroader peaks than those same materials post-heat treatment orpost-calcination. Such variability is reflected, in part, by anydifferences in the various XRD patterns described in the instantapplication. The person of skill in the art in this area wouldappreciate the significance of any such variations.

A single cell crystal structure has been analyzed as described in theExamples, whose structural characteristics are described there. So, instill other embodiments, the crystalline compositions exhibit unit cellparameters substantially equal or equivalent to the following:

Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V(Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)

Crystallographic evidence also has shown that the channel dimensions ofthe 10- and 14-membered rings are 6.2×4.5 Å and 9.1×7.2 Å, respectively.Additionally, in some embodiments, the crystalline framework may have adensity of 16.4 tetrahedral atoms (“T-atoms”) per nm³.

In certain embodiments, the crystalline compositions of the present canhave a ratio of Si:Ge atoms within any one or more of the ranges of from1:1 to 2:1 (or lower), from 2:1 to 3:1, from 3:1 to 4:1, from 4:1 to5:1, from 5:1 to 6:1, from 6:1 to 7:1, from 7:1 to 8:1, from 8:1 to 9:1,from 9:1 to 10:1, from 10:1 to 11:1, from 11:1 to 12:1, from 12:1 to13:1, from 13:1 to 14:1, from 14:1 to 15:1, from 15:1 to 16:1 or higher.As shown in FIG. 12(B), and the supporting XRD patterns, high puritieshave been achieved throughout the range of ratios of from about 4:1 toabout 16:1.

Depending on the processing of the crystalline compositions, thesecompositions may contain the organic structuring agent (OSDA) used intheir preparation, or may be substantially free or devoid of any suchOSDA (the terms “substantially” and “substantially devoid” are analogousto the term “OSDA depleted” described elsewhere herein). The specificstructuring agents used to prepare these crystalline compositions arealso described elsewhere herein.

The presence of these OSDAs may be identified using, for example, ¹³CNMR or any of the methods defined in the Examples. It is a particularfeature of the present invention that the cationic OSDAs retain theiroriginal structures, including their stereochemical conformations duringthe synthetic processes, these structures being compromised during thesubsequent calcinations or oxidative treatments.

In some embodiments, where HF or other source of fluoride is used thatthe mineralizing agent, the pores may additionally comprise fluoride (asevidenced by ¹⁹F NMR). In other embodiments, either when usingmineralizing agents not containing fluoride or otherwise if anypotential fluoride flushed or displaced from compositions, thecompositions are substantially fluoride-free.

The disclosed crystalline microporous germanosilicate compositionsinclude those which result from the post-treatment or further processingdescribed in the following Methods section of this disclosure. Theseinclude germanosilicates in their hydrogen forms or those havingcations, metals or metal oxides within their pore structures.Accordingly, in certain embodiments, the microporous pure or substitutedgermanosilicates contain Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga,In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, orR_(4-n)N⁺H_(n) cations, where R is alkyl, n=0-4 in at least some oftheir pores. In specific aspects of these embodiments, these porescontain NaCl or KCl.

Additional embodiments include those crystalline microporous solids ofthe present disclosure, at least some of whose pores transition metals,transition metal oxides, or salts, said metals including, for examplescandium, yttrium, titanium, zirconium, vanadium, manganese, chromium,molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium,nickel, palladium, platinum, copper, silver, gold, or mixtures thereof,each as a metal, oxide, or salt. In one specific embodiment, the poresof the germanosilicate solids contain copper, as metal, oxide, or salt.

Methods of Preparing the Inventive Compositions

Certain embodiments of the present disclosure include methods forpreparing crystalline microporous germanosilicate compositions, eachmethod comprising hydrothermally treating an aqueous compositioncomprising:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one substituted benzyl-imidazolium organicstructure-directing agent (OSDA) having a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C₁₋₃ alkyl, preferable where R¹, R²,and R³ are independently ethyl or methyl, more preferably where R¹, R²,and R³ are methyl, under conditions effective to crystallize acrystalline microporous germanosilicate composition having a structureor exhibiting a characteristic associated with the inventivecompositions.

The source of silicon oxide, as described above, may comprise asilicate, silica hydrogel, silicic acid, fumed silica, colloidal silica,tetra-alkyl orthosilicate, a silica hydroxide or combination thereof.Sodium silicate or tetraorthosilicates, for example tetraethylorthosilicate (TEOS), are preferred sources. The sources of siliconoxide may be amorphous (i.e., the XRD pattern of the solid showinglittle or no structure), microcrystalline (i.e., the XRD pattern of thesolid showing broadened reflectance peaks indicative of a small degreeof long range order), or crystalline (i.e., the XRD pattern of the solidshowing well defined and sharp reflectance peaks).

Sources of germanium oxide can include alkali metal orthogermanates,M₄GeO₄, containing discrete GeO₄ ⁴⁻ ions, GeO(OH)₃ ⁻, GeO₂(OH)₂ ²⁻,[(Ge(OH)₄)₈(OH)₃]³⁻ or neutral solutions of germanium dioxide containGe(OH)₄, or alkoxide or carboxylate derivatives thereof.

Where the aqueous composition is free from any of the optional sourcesof metal oxides, the process yields pure crystalline microporouspure-germanosilicate materials, the term “pure” reflecting the absenceof all but the inevitable impurities present in the sources of siliconor germanium oxides. The aqueous compositions may also comprise othersources of metal oxide, deliberately added, for example sources ofaluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide,tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide,or combination or mixture thereof, in which case the resulting productmay contain the corresponding metal oxide within the resulting latticeframework.

In preparing the germanosilicates, the silicon oxide and the source ofgermanium oxide are present in a molar ratio of Si:Ge in a range of fromabout 2:1 to about 8:1. Higher and lower ratios may also be used, thoughthese tend to result in final product of lesser purities. In someembodiments, the molar ratio of Ge:Si is in at least one range of from2:1 to 3:1, from 3:1 to 4:1, from 4:1 to 5:1, from 5:1 to 6:1, from 6:1to 7:1, from 7:1 to 8:1, for example 3:1 to 8:1.

In some embodiments, the mineralizing agent comprises an aqueous alkalimetal or alkaline earth metal hydroxide, thereby rendering thesecompositions alkaline. In certain of these embodiments, the alkali metalor alkaline earth metal hydroxide include LiOH, NaOH, KOH, RbOH, CsOH,Mg(OH)₂, Ca(OH)₂, Sr(OH)₂, or Ba(OH)₂. LiOH, NaOH, or KOH appear to bepreferred. In some cases, the pH of the water is in a range of from 7 to14, or greater. Under these conditions, the oxide precursors can beexpected to be at least partially hydrated to their hydroxide forms.

In other embodiments, the mineralizing agent is or comprises a source offluoride ion. Aqueous hydrofluoric acid is particularly suitable forthis purpose, whether used as provided, or generated in situ by otherconventional methods. Such sources of HF can include:

(a) aqueous ammonium hydrogen fluoride (NH₄F.HF) or ammonium fluorideitself;

(b) an alkali metal bifluoride salt (i.e., MHF₂, where M^(|) is Li^(|),Na^(|), or K^(|)), or a combination thereof; or

(c) at least one fluoride salt, such as an alkali metal, alkaline earthmetal, or ammonium fluoride salt (e.g., LiF, NaF, KF, CsF, CaF₂,tetraalkyl ammonium fluoride (e.g., tetramethyl ammonium fluoride)) inthe presence of at least one mineral acid that is stronger than HF(e.g., HCl, HBr, HI, H₃PO₄, HNO₃, oxalic acid, or H₂SO₄) and can reactwith fluorides to form HF in situ; or

(d) a combination of two or more of (a)-(c). Within these systems, atleast, volatile sources of fluoride (e.g., HF, NH₄F, or NH₄F.HF) arepreferred.

The OSDAs may be described in the context of

but not

with the various options described for R² and R³ described above andelsewhere herein. As shown in the Examples, the cleanest CIT-13materials appear to be prepared from OSDAs in which the R³ substituentsare positioned meta to the benzylic linkage, for example:

In certain embodiments, the substituted imidazolium portion of the OSDAcomprises:

In certain embodiments, the substituted benzyl-imidazolium organicstructure-directing agent has a structure:

where n, R¹, R², and R³ are any of the embodiments described elsewhereherein.

In more specific embodiments, the at least one substitutedbenzyl-imidazolium organic structure-directing agent has a structure(each structure being considered an independent embodiment):

The counterion to the OSDA's described herein, at least as added to thereaction mixture, are typically bromide, chloride, fluoride, iodide, orhydroxide ion, but the OSDA may be added also to the composition as anacetate, nitrate, or sulfate. In some embodiments, the quaternary cationhas an associated fluoride or hydroxide ion, preferably substantiallyfree of other halide counterions. In separate embodiments, theassociated anion is hydroxide.

The processes and compositions may further be defined in terms of theratios of other of the individual ingredients. In certain embodiments,the molar ratio of the OSDA:Si is in a range of from 0.1 to 0.15, from0.15 to 0.2, from 0.2 to 0.25, from 0.25 to 0.3, from 0.3 to 0.35, from0.35 to 0.4, from 0.4 to 0.45, from 0.45 to 0.5, from 0.5 to 0.55, from0.55 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7, from 0.7 to 0.75, from0.75 to 0.8, from 0.8 to 0.85, from 0.85 to 0.9, from 0.9 to 0.95, from0.95 to 1, or a range combining any two or more of these ranges, forexample from 0.4 to 0.6 or from 0.4 to 0.75.

In other embodiments, the molar ratio of water:Si is in a range of fromabout 2 to 3 (i.e., 2:1 to 3:1), from 3 to 4, from 4 to 5, from 5 to 6,from 6 to 7, from 7 to 8, from 8 to 9, from 9 to 10, from 10 to 11, from11 to 12, from 12 to 13, from 13 to 14, from 14 to 15, from 15 to 16,from 16 to 17, from 17 to 18, from 18 to 19, from 19 to 20, or a rangecombining any two or more of these ranges, for example in a range offrom about 2 to about 10, from about 3 to 10, or from 3 to 8.

Where the mineralizing agent is a fluoride source, such as HF, the molarratio of fluoride:Si may be in a range of from about 0.1 to 0.15, from0.15 to 0.2, from 0.2 to 0.25, from 0.25 to 0.3, from 0.3 to 0.35, from0.35 to 0.4, from 0.4 to 0.45, from 0.45 to 0.5, from 0.5 to 0.55, from0.55 to 0.6, from 0.6 to 0.65, from 0.65 to 0.7, from 0.7 to 0.75, or arange combining any two or more of these ranges, for example in a rangeof from about 0.4 to about 0.6.

To this point, the processes have been defined in terms of conditionsunder conditions effective to crystallize a crystalline microporousgermanosilicates of CIT-13 topology. In light of the other teachingswithin this disclosure, this is believed to be a sufficient description.But in certain aspects of this, these conditions include treatment ofthe respective hydrothermally treated aqueous composition at atemperature defined by at least one range of from 100° C. to 110° C.,from 110° C. to 120° C., from 120° C. to 125° C., from 125° C. to 130°C., from 130° C. to 135° C., from 135° C. to 140° C., from 140° C. to145° C., from 145° C. to 150° C., from 150° C. to 155° C., from 155° C.to 160° C., from 160° C. to 165° C., from 165° C. to 170° C., from 170°C. to 175° C., from 175° C. to 180° C., from 180° C. to 185° C., from185° C. to 190° C., from 190° C. to 195° C., from 195° C. to 200° C.,for example, from 120° C. to 160° C. In related embodiments, the timesof this treatment, while dependent on the specific reaction conditions(e.g., temperatures and concentrations), can range from 3 to 40 days,preferably from 7 to 40 days. These ranges provide for convenientreaction times, though higher and lower temperatures and longer orshorter times may also be employed. This hydrothermal treating is alsotypically done in a sealed autoclave, at autogenous pressures.Additional exemplary reaction conditions are provided in the Examples.

As discussed at least in the Examples, the synthesis of novelextra-large-pore framework CIT-13 has been demonstrated in a wide rangeof synthetic variables. Using the monoquaternary OSDAs belonging to themethylbenzylimidazolium family and the dimethylbenzylimidazolium family,an optimized condition for CIT-13 is suggested as follows: the gelcomposition at Si/Ge=3-8, H₂O/T=5-7.5 (where “T” refers to the totalnumber of Si and Ge atoms); OSDA+F−/T=0.5 using1-methyl-3-(3,5-dimethylbenzyl)imidazolium or1,2-dimethyl-3-(3-methylimidazolium as the OSDA in a 140° C.-180° C.static/rotating oven for 1-3 weeks.

In some embodiments the reaction mixture, which may be a suspension or agel, or a gelling suspension, can be subjected to mild stirring orrolling agitation during crystallization. It will be understood by aperson skilled in the art that the as produced crystalline microporoussolid s described herein can contain impurities, such as amorphousmaterials, or materials having framework topologies which do notcoincide with the targeted or desired product. During hydrothermalcrystallization, the crystals can be allowed to nucleate spontaneouslyfrom the reaction mixture.

The use of crystals of the desired crystalline product as seed materialcan result in decreasing the time necessary for complete crystallizationto occur. In addition, seeding can lead to an increased purity of theproduct obtained by promoting the nucleation and/or formation of themolecular sieve over any undesired phases. When used as seeds, seedcrystals are added in an amount between 0.01% and 10%, for example, 1%,of the mass of the total amount of oxide in the reaction mixture. Thetotal amount of oxide refers to the total mass of oxides in the reactionmixture gel prior to heating, present as the oxides or oxide sources.

Once the initially-formed crystalline solids of the CIT-13 topology areprepared (e.g., including pure or substituted germanosilicates), furtherembodiments comprise isolating these solids. These crystalline solidsmay be removed from the reaction mixtures by any suitable means (e.g.,filtration, centrifugation, etc. or simple removal of the membranetemplate) and dried. Such drying may be done in air or under vacuum attemperatures ranging from 25° C. to about 200° C. Typically, such dryingis done at a temperature of about 100° C.

As shown in the various Examples, the methods described herein produceor are capable of producing compositionally “clean” crystallinemicroporous materials. That is, in various embodiments, the crystallinemicroporous materials described herein are at least 75%, 80%, 85%, 90%,95%, or 98% by weight of the nominal topology. In some embodiments, thecrystalline microporous materials are sufficiently clean as to exhibitXRD patterns where other crystalline topologies are undetectable.

The crystalline microporous germanosilicate solid products, at least asinitially isolated, typically contain amounts of the OSDAs used in theirsyntheses occluded in their pores, and these can be detected by NMR orinferred by TGA weight loss profiles, some of which are describedfurther in the Examples. These isolated solids also may exhibit powerXRD patterns consistent with the structures described herein, perhaps asbroadened patterns. Residual OSDAs may be removed from the pores of theisolated solids by any number of suitable methods, for example:

(a) heating the isolated product solid at a temperature in a range offrom about 250° C. to about 450° C. in an oxidizing atmosphere, such asair or oxygen, or in an inert atmosphere, such as argon or nitrogen; or

(b) contacting the isolated product solid with ozone or other oxidizingagent at a temperature in a range of 25° C. to 200° C.;

for a time sufficient to form a dehydrated or an OSDA-depleted product.The resulting crystalline germanosilicate products are thensubstantially devoid of residual OSDA.

As used herein, the term “OSDA-depleted” (or composition having depletedOSDA) refers to a composition having a lesser content of OSDA after thetreatment than before. In preferred embodiments, substantially all(e.g., greater than 90, 95, 98, 99, or 99.5 wt %) or all of the OSDA isremoved by the treatment. In some embodiments, this can be confirmed bythe absence of a TGA endotherm associated with the removal of the OSDAwhen the product material is subject to TGA analysis or the absence orsubstantial absence of C or N in elemental analysis (prior to heating,expect composition to comprise C, N, O, Si, Al, H).

In those embodiments where the processing involved heating, typicalheating rates include is 0.1° C. to 10° C. per minute and or 0.5° C. to5° C. per minute. Different heating rates may be employed depending onthe temperature range. Depending on the nature of the calciningatmosphere, the materials may be heated to the indicated temperaturesfor periods of time ranging from 1 to 60 hours or more, to produce acatalytically active product.

The ozone-treatment can be carried out in a flow of ozone-containingoxygen (typically for 6 hours or more. but shorter could be feasible).Practically any oxidative environment sufficient to remove the OSDA canbe used, especially those already known for this purpose. Suchenvironments, for example, can involve the use of organic oxidizers(alkyl or aryl peroxides or peracids) or inorganic peroxides (e.g.,H₂O₂) (alkyl or aryl peroxides or peracids.

Further processing of these materials, whether modified or not, may alsocomprise, heating the isolated crystalline microporous germanosilicatesolid at a temperature in a range of from about 200° C. to about 600° C.in the presence of an alkali, alkaline earth, transition metal, rareearth metal, ammonium or alkylammonium salts (anions including halide,preferable chloride, nitrate, sulfate, phosphate, carboxylate, ormixtures thereof) for a time sufficient to form a dehydrated or anOSDA-depleted product. In certain of these embodiments, the heating isdone in the presence of NaCl or KCl. In certain exemplary embodiments,the heating is done at a temperature in a range of from 500 to 600° C.In exemplary embodiments, the heating is done in either an oxidizing orinert atmosphere.

These crystalline microporous solids may be further modified, forexample, by incorporating metals with the pore structures, either beforeor after drying, for example by replacing some of the cations in thestructures with additional metal cations using techniques known to besuitable for this purpose (e.g., ion exchange). Such cations can includethose of rare earth, Group 1, Group 2 and transition metals, for exampleCa, Cd, Co, Cu, Fe, Mg, Mn, Ni, Pt, Pd, Re, Sn, Ti, V, W, Zn and theirmixtures. In other specific embodiments, the metal cation salt is acopper salt, for example, Schweizer's reagent (tetraamminediaquacopperdihydroxide, [Cu(NH₃)₄(H₂O)₂](OH)₂]), copper(II) nitrate, or copper(II)carbonate.

The addition of a transition metal or transition metal oxide may beaccomplished, for example by chemical vapor deposition or chemicalprecipitation. As used herein, the term “transition metal” refers to anyelement in the d-block of the periodic table, which includes groups 3 to12 on the periodic table, as well as the elements of the f-blocklanthanide and actinide series. This definition of transition metalsspecifically encompasses Group 4 to Group 12 elements. In certain otherindependent embodiments, the transition metal or transition metal oxidecomprises an element of Groups 6, 7, 8, 9, 10, 11, or 12. In still otherindependent embodiments, the transition metal or transition metal oxidecomprises scandium, yttrium, titanium, zirconium, vanadium, manganese,chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt,rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, ormixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixturesthereof are preferred dopants.

In other embodiments, the optionally doped crystalline solids arecalcined in air a temperature defined as being in at least one range offrom 400° C. to 500° C., from 500° C. to 600° C., from 600° C. to 700°C., from 700° C. to 800° C., from 800° C. to 900° C., from 900° C. to1000° C., from 1000° C. to 1200° C., 500° C. to about 1200° C.

Intermediate Reaction Compositions

As described herein, the as-formed and post-treated crystallinegermanosilicate compositions themselves are within the scope of thepresent disclosure and are considered to be independent embodiments ofthe present invention. All of the descriptions used to describe thefeatures of the disclosed processes yield compositions which areseparately considered embodiments. In an abundance of caution, some ofthese are presented here, but these descriptions should not beconsidered to exclude embodiments provided or which naturally followfrom other descriptions.

These embodiments include compositions comprising the aqueouscompositions used in the hydrothermal treatments together with therespective crystalline microporous seed or product germanosilicates,wherein the germanosilicate products contain the respective OSDAs usedin their preparation occluded in their pores.

For example, in some embodiments, the composition comprises:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one of the substituted benzyl-imidazolium organicstructure-directing agent (OSDA) described above, including at least onehaving a structure:

but not

wherein m, n, R¹, R², and R³ are as identified above and elsewhereherein; and

(e) a crystalline microporous germanosilicate compositionally consistentwith the CIT-13 topology, or a seed thereof.

As used herein, the term “compositionally consistent” refers to acrystalline germanosilicate composition having a stoichiometryconsistent with one resulting from the at least a partial progression ofthe hydrothermal treating process used to prepare these materials.Typically, these compositionally consistent crystalline microporous pureor optionally substituted germanosilicate typically contain, occluded intheir pores, the OSDA used to make them; i.e., the OSDA present in theassociated aqueous compositions. In separate embodiments, thesecompositionally consistent crystalline solids may also be substantiallyfree of the OSDAs used in the aqueous media; in such embodiments, theoptionally substituted germanosilicates may be used as seed material forthe crystallization, also as described elsewhere herein.

These compositions may comprise any of the types, sources, and ratios ofingredients associated with a process described elsewhere herein, andmay exist at any temperature consistent with the processing conditionsdescribed above as useful for the hydrothermal processing embodiments.It should be appreciated that this disclosure captures each and every ofthese permutations as separate embodiments, as if they were separatelylisted.

In some embodiments, these compositions exist in the form of asuspension. In other embodiments, these compositions exist in the formof a gel.

Uses of the Inventive Compositions

In various embodiments, the crystalline microporous germanosilicatesolids of the present invention, calcined, doped, or treated with thecatalysts described herein, mediate or catalyze an array of chemicaltransformation. Such transformations may include carbonylating DME withCO at low temperatures, reducing NOx with methane (e.g., in exhaustapplications), cracking, hydrocracking, dehydrogenating, convertingparaffins to aromatics, MTO, isomerizing aromatics (e.g., xylenes),disproportionating aromatics (e.g., toluene), alkylating aromatichydrocarbons, oligomerizing alkenes, aminating lower alcohols,separating and sorbing lower alkanes, hydrocracking a hydrocarbon,dewaxing a hydrocarbon feedstock, isomerizing an olefin, producing ahigher molecular weight hydrocarbon from lower molecular weighthydrocarbon, reforming a hydrocarbon, converting lower alcohol or otheroxygenated hydrocarbons to produce olefin products, epoxiding olefinswith hydrogen peroxide, reducing the content of an oxide of nitrogencontained in a gas stream in the presence of oxygen, or separatingnitrogen from a nitrogen-containing gas mixture by contacting therespective feedstock with the a catalyst comprising the crystallinemicroporous solid of any one of materials described herein underconditions sufficient to affect the named transformation. Particularlyattractive applications include in which these germanosilicates areexpected to be useful include catalytic cracking, hydrocracking,dewaxing, alkylation, and olefin and aromatics formation reactions.Additional applications include gas drying and separation.

Specific embodiments provide hydrocracking processes, each processcomprising contacting a hydrocarbon feedstock under hydrocrackingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form.

Still other embodiments provide processes for dewaxing hydrocarbonfeedstocks, each process comprising contacting a hydrocarbon feedstockunder dewaxing conditions with a catalyst comprising a crystallinemicroporous solid of this invention. Yet other embodiments provideprocesses for improving the viscosity index of a dewaxed product of waxyhydrocarbon feeds, each process comprising contacting the waxyhydrocarbon feed under isomerization dewaxing conditions with a catalystcomprising a crystalline microporous solid of this invention.

Additional embodiments include those process for producing a C20+ lubeoil from a C20+ olefin feed, each process comprising isomerizing saidolefin feed under isomerization conditions over a catalyst comprising atleast one transition metal catalyst and a crystalline microporous solidof this invention.

Also included in the present invention are processes for isomerizationdewaxing a raffinate, each process comprising contacting said raffinate,for example a bright stock, in the presence of added hydrogen with acatalyst comprising at least one transition metal and a crystallinemicroporous solid of this invention.

Other embodiments provide for dewaxing a hydrocarbon oil feedstockboiling above about 350° F. and containing straight chain and slightlybranched chain hydrocarbons comprising contacting said hydrocarbon oilfeedstock in the presence of added hydrogen gas at a hydrogen pressureof about 15-3000 psi with a catalyst comprising at least one transitionmetal and a crystalline microporous solid of this invention, preferablypredominantly in the hydrogen form.

Also included in the present invention is a process for preparing alubricating oil which comprises hydrocracking in a hydrocracking zone ahydrocarbonaceous feedstock to obtain an effluent comprising ahydrocracked oil, and catalytically dewaxing said effluent comprisinghydrocracked oil at a temperature of at least about 400° F. and at apressure of from about 15 psig to about 3000 psig in the presence ofadded hydrogen gas with a catalyst comprising at least one transitionmetal and a crystalline microporous solid of this invention.

Also included in this invention is a process for increasing the octaneof a hydrocarbon feedstock to produce a product having an increasedaromatics content, each process comprising contacting ahydrocarbonaceous feedstock which comprises normal and slightly branchedhydrocarbons having a boiling range above about 40° C. and less thanabout 200° C., under aromatic conversion conditions with a catalystcomprising a crystalline microporous solid of this invention. In theseembodiments, the crystalline microporous solid is preferably madesubstantially free of acidity by neutralizing said solid with a basicmetal. Also provided in this invention is such a process wherein thecrystalline microporous solid contains a transition metal component.

Also provided by the present invention are catalytic cracking processes,each process comprising contacting a hydrocarbon feedstock in a reactionzone under catalytic cracking conditions in the absence of addedhydrogen with a catalyst comprising a crystalline microporous solid ofthis invention. Also included in this invention is such a catalyticcracking process wherein the catalyst additionally comprises anadditional large pore crystalline cracking component.

This invention further provides isomerization processes for isomerizingC4 to C7 hydrocarbons, each process comprising contacting a feed havingnormal and slightly branched C4 to C hydrocarbons under isomerizingconditions with a catalyst comprising a crystalline microporous solid ofthis invention, preferably predominantly in the hydrogen form. Thecrystalline microporous solid may be impregnated with at least onetransition metal, preferably platinum. The catalyst may be calcined in asteam/air mixture at an elevated temperature after impregnation of thetransition metal.

Also provided by the present invention are processes for alkylating anaromatic hydrocarbon, each process comprising contacting underalkylation conditions at least a molar excess of an aromatic hydrocarbonwith a C2 to C20 olefin under at least partial liquid phase conditionsand in the presence of a catalyst comprising a crystalline microporoussolid of this invention, preferably predominantly in the hydrogen form.The olefin may be a C2 to C4 olefin, and the aromatic hydrocarbon andolefin may be present in a molar ratio of about 4:1 to about 20:1,respectively. The aromatic hydrocarbon may be selected from the groupconsisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof.

Further provided in accordance with this invention are processes fortransalkylating an aromatic hydrocarbon, each of which process comprisescontacting under transalkylating conditions an aromatic hydrocarbon witha polyalkyl aromatic hydrocarbon under at least partial liquid phaseconditions and in the presence of a catalyst comprising a crystallinemicroporous solid of this invention, preferably predominantly in thehydrogen form. The aromatic hydrocarbon and the polyalkyl aromatichydrocarbon may be present in a molar ratio of from about 1:1 to about25:1, respectively. The aromatic hydrocarbon may be selected from thegroup consisting of benzene, toluene, ethylbenzene, xylene, or mixturesthereof, and the polyalkyl aromatic hydrocarbon may be a dialkylbenzene.

Further provided by this invention are processes to convert paraffins toaromatics, each of which process comprises contacting paraffins underconditions which cause paraffins to convert to aromatics with a catalystcomprising a crystalline microporous solid of this invention, saidcatalyst comprising gallium, zinc, or a compound of gallium or zinc.

In accordance with this invention there is also provided processes forisomerizing olefins, each process comprising contacting said olefinunder conditions which cause isomerization of the olefin with a catalystcomprising a crystalline microporous solid of this invention.

Further provided in accordance with this invention are processes forisomerizing an isomerization feed, each process comprising an aromaticC8 stream of xylene isomers or mixtures of xylene isomers andethylbenzene, wherein a more nearly equilibrium ratio of ortho-,meta-and para-xylenes is obtained, said process comprising contactingsaid feed under isomerization conditions with a catalyst comprising acrystalline microporous solid of this invention.

The present invention further provides processes for oligomerizingolefins, each process comprising contacting an olefin feed underoligomerization conditions with a catalyst comprising a crystallinemicroporous solid of this invention.

This invention also provides processes for converting lower alcohols andother oxygenated hydrocarbons, each process comprising contacting saidlower alcohol (for example, methanol, ethanol, or propanol) or otheroxygenated hydrocarbon with a catalyst comprising a crystallinemicroporous solid of this invention under conditions to produce liquidproducts.

Also provided by the present invention are processes for reducing oxidesof nitrogen contained in a gas stream in the presence of oxygen whereineach process comprises contacting the gas stream with a crystallinemicroporous solid of this invention. The a crystalline microporous solidmay contain a metal or metal ions (such as cobalt, copper or mixturesthereof) capable of catalyzing the reduction of the oxides of nitrogen,and may be conducted in the presence of a stoichiometric excess ofoxygen. In a preferred embodiment, the gas stream is the exhaust streamof an internal combustion engine.

Also provided are processes for converting synthesis gas containinghydrogen and carbon monoxide, also referred to as syngas or synthesisgas, to liquid hydrocarbon fuels, using a catalyst comprising any of thegermanosilicates described herein, including those having CIT-13frameworks, and Fischer-Tropsch catalysts. Such catalysts are describedin U.S. Pat. No. 9,278,344, which is incorporated by reference for itsteaching of the catalysts and methods of using the catalysts. TheFischer-Tropsch component includes a transition metal component ofgroups 8-10 (i.e., Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), preferablycobalt, iron and/or ruthenium. The optimum amount of catalyticallyactive metal present depends inter alia on the specific catalyticallyactive metal. Typically, the amount of cobalt present in the catalystmay range from 1 to 100 parts by weight per 100 parts by weight ofsupport material, preferably from 10 to 50 parts by weight per 100 partsby weight of support material. In one embodiment, from 15 to 45 wt %cobalt is deposited on the hybrid support as the Fischer-Tropschcomponent. In another embodiment from 20 to 45 wt % cobalt is depositedon the hybrid support. The catalytically active Fischer-Tropschcomponent may be present in the catalyst together with one or more metalpromoters or co-catalysts. The promoters may be present as metals or asmetal oxide, depending upon the particular promoter concerned. Suitablepromoters include metals or oxides of transition metals, includinglanthanides and/or the actinides or oxides of the lanthanides and/or theactinides. As an alternative or in addition to the metal oxide promoter,the catalyst may comprise a metal promoter selected from Groups 7 (Mn,Tc, Re) and/or Groups 8-10. In some embodiments, the Fischer-Tropschcomponent further comprises a cobalt reduction promoter selected fromthe group consisting of platinum, ruthenium, rhenium, silver andcombinations thereof. The method employed to deposit the Fischer-Tropschcomponent on the hybrid support involves an impregnation technique usingaqueous or non-aqueous solution containing a soluble cobalt salt and, ifdesired, a soluble promoter metal salt, e.g., platinum salt, in order toachieve the necessary metal loading and distribution required to providea highly selective and active hybrid synthesis gas conversion catalyst.

Still further process embodiments include those for reducing halideconcentration in an initial hydrocarbon product comprising undesirablelevels of an organic halide, the process comprising contacting at leasta portion of the hydrocarbon product with a composition comprising anyof the germanosilicate structures described herein, including CIT-13,under organic halide absorption conditions to reduce the halogenconcentration in the hydrocarbon. The initial hydrocarbon product may bemade by a hydrocarbon conversion process using an ionic liquid catalystcomprising a halogen-containing acidic ionic liquid. In someembodiments, the organic halid content in the initial hydrocarbonproduct is in a range of from 50 to 4000 ppm; in other embodiments, thehalogen concentrations are reduced to provide a product having less than40 ppm. In other embodiments, the production may realize a reduction of85%, 90%, 95%, 97%, or more. The initial hydrocarbon stream may comprisean alkylate or gasoline alkylate. Preferably the hydrocarbon alkylate oralkylate gasoline product is not degraded during the contacting. Any ofthe materials or process conditions described in U.S. Pat. No. 8,105,481are considered to describe the range of materials and process conditionsof the present invention. U.S. Pat. No. 8,105,481 is incorporated byreference at least for its teachings of the methods and materials usedto effect such transformations (both alkylations and halogenreductions).

Still further process embodiments include those processes for increasingthe octane of a hydrocarbon feedstock to produce a product having anincreased aromatics content comprising contacting a hydrocarbonaceousfeedstock which comprises normal and slightly branched hydrocarbonshaving a boiling range above about 40 C and less than about 200 C underaromatic conversion conditions with the catalyst.

Specific conditions for many of these transformations are known to thoseof ordinary skill in the art. Exemplary conditions for suchreactions/transformations may also be found in WO/1999/008961, U.S. Pat.Nos. 4,544,538, 7,083,714, 6,841,063, and 6,827,843, each of which areincorporated by reference herein in its entirety for at least thesepurposes.

Depending upon the type of reaction which is catalyzed, the microporoussolid may be predominantly in the hydrogen form, partially acidic orsubstantially free of acidity. The skilled artisan would be able todefine these conditions without undue effort. As used herein,“predominantly in the hydrogen form” means that, after calcination(which may also include exchange of the pre-calcined material with NH₄₊prior to calcination), at least 80% of the cation sites are occupied byhydrogen ions and/or rare earth ions.

The germanosilicates of the present invention may also be used asadsorbents for gas separations. For example, these germanosilicate canalso be used as hydrocarbon traps, for example, as a cold starthydrocarbon trap in combustion engine pollution control systems. Inparticular, such germanosilicate may be particularly useful for trappingC₃ fragments. Such embodiments may comprise processes and devices fortrapping low molecular weight hydrocarbons from an incoming gas stream,the process comprising passing the gas stream across or through acomposition comprising any one of the crystalline microporousgermanosilicate compositions described herein, so as to provide anoutgoing gas stream having a reduced concentration of low molecularweight hydrocarbons relative to the incoming gas stream. In thiscontext, the term “low molecular weight hydrocarbons” refers to C1-C6hydrocarbons or hydrocarbon fragments.

The germanosilicates of the present invention may also be used in aprocess for treating a cold-start engine exhaust gas stream containinghydrocarbons and other pollutants, wherein the process comprises orconsist of flowing the engine exhaust gas stream over one of thegermanosilicate compositions of the present invention whichpreferentially adsorbs the hydrocarbons over water to provide a firstexhaust stream, and flowing the first exhaust gas stream over a catalystto convert any residual hydrocarbons and other pollutants contained inthe first exhaust gas stream to innocuous products and provide a treatedexhaust stream and discharging the treated exhaust stream into theatmosphere.

The germanosilicates of the present invention can also be used toseparate gases. For example, these can be used to separate water, carbondioxide, and sulfur dioxide from fluid streams, such as low-gradenatural gas streams, and carbon dioxide from natural gas. Typically, themolecular sieve is used as a component in a membrane that is used toseparate the gases. Examples of such membranes are disclosed in U.S.Pat. No. 6,508,860.

For each of the preceding processes described, additional correspondingembodiments include those comprising a device or system comprising orcontaining the materials described for each process. For example, in thegas of the gas trapping, additional embodiments include those devicesknown in the art as hydrocarbon traps which may be positioned in theexhaust gas passage of a vehicle. In such devices, hydrocarbons areadsorbed on the trap and stored until the engine and exhaust reach asufficient temperature for desorption. The devices may also comprisemembranes comprising the germanosilicate compositions, useful in theprocesses described.

Terms

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the invention whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the invention that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting” of excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps “and those that do not materially affect the basic and novelcharacteristic(s)” of the claimed invention. Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially of” For those embodimentsprovided in terms of “consisting essentially of” the basic and novelcharacteristic(s) is the facile operability of the methods orcompositions/systems to provide the germanosilicate compositions atmeaningful yields (or the ability of the systems using only thoseingredients listed.

The term “meaningful product yields” is intended to reflect productyields such as described herein, but also including greater than 20%,but when specified, this term may also refer to yields of 10%, 20%, 30%,40%, 50%, 60%, 70%, 80%, or 90% or more, relative to the amount oforiginal substrate.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C,” as separate embodiments, as well as C₁₋₃.

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The term “alkyl” as used herein refers to a linear, branched, or cyclicsaturated hydrocarbon group typically although not necessarilycontaining 1 to about 6 carbon atoms, such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, and the like.

The term “aromatic” refers to the ring moieties which satisfy the Hückel4n+2 rule for aromaticity, and includes both aryl (i.e., carbocyclic)and heteroaryl structures.

The term “halide” is used in the conventional sense to refer to achloride, bromide, fluoride, or iodide.

“Lower alcohols” or lower alkanes refer to alcohols or alkanes,respectively, having 1-10 carbons, linear or branched, preferably 1-6carbon atoms and preferably linear. Methanol, ethanol, propanol,butanol, pentanol, and hexanol are examples of lower alcohols. Methane,ethane, propane, butane, pentane, and hexane are examples of loweralkanes.

The terms “oxygenated hydrocarbons” or “oxygenates” as known in the artof hydrocarbon processing to refer to components which include alcohols,aldehydes, carboxylic acids, ethers, and/or ketones which are known tobe present in hydrocarbon streams or derived from biomass streams othersources (e.g. ethanol from fermenting sugar).

The terms “separating” or “separated” carry their ordinary meaning aswould be understood by the skilled artisan, insofar as they connotephysically partitioning or isolating solid product materias from otherstarting materials or co-products or side-products (impurities)associated with the reaction conditions yielding the material. As such,it infers that the skilled artisan at least recognizes the existence ofthe product and takes specific action to separate or isolate it fromstarting materials and/or side- or byproducts. Absolute purity is notrequired, though it is preferred. In the case where the terms are usedin the context of gas processing, the terms “separating” or “separated”connote a partitioning of the gases by adsorption or by permeation basedon size or physical or chemical properties, as would be understood bythose skilled in the art.

Unless otherwise indicated, the term “isolated” means physicallyseparated from the other components so as to be free of at leastsolvents or other impurities, such as starting materials, co-products,or byproducts. In some embodiments, the isolated crystalline materials,for example, may be considered isolated when separated from the reactionmixture giving rise to their preparation, from mixed phase co-products,or both. In some of these embodiments, pure germanosilicates (includingstructures with or without incorporated OSDAs) can be made directly fromthe described methods. In some cases, it may not be possible to separatecrystalline phases from one another, in which case, the term “isolated”can refer to separation from their source compositions.

The term “microporous,” according to IUPAC notation refers to a materialhaving pore diameters of less than 2 nm. Similarly, the term“macroporous” refers to materials having pore diameters of greater than50 nm. And the term “mesoporous” refers to materials whose pore sizesare intermediate between microporous and macroporous. Within the contextof the present disclosure, the material properties and applicationsdepend on the properties of the framework such as pore size anddimensionality, cage dimensions and material composition. Due to thisthere is often only a single framework and composition that givesoptimal performance in a desired application.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

The terms “method(s)” and “process(es)” are considered interchangeablewithin this disclosure.

As used herein, the term “crystalline microporous solids” or“crystalline microporous germanosilicate” are crystalline structureshaving very regular pore structures of molecular dimensions, i.e., under2 nm. The maximum size of the species that can enter the pores of acrystalline microporous solid is controlled by the dimensions of thechannels. These terms may also refer specifically to CIT-13compositions.

The term “silicate” refers to any composition including silicate (orsilicon oxide) within its framework. It is a general term encompassing,for example, pure-silica (i.e., absent other detectable metal oxideswithin the framework), aluminosilicate, borosilicate, ferrosilicate,germanosilicate, stannosilicate, titanosilicate, or zincosilicatestructures. The term “germanosilicate” refers to any compositionincluding silicon and germanium oxides within its framework. Suchgermanosilicate may be “pure-germanosilicate (i.e., absent otherdetectable metal oxides within the framework) or optionally substituted.When described as “optionally substituted,” the respective framework maycontain aluminum, boron, gallium, germanium, hafnium, iron, tin,titanium, indium, vanadium, zinc, zirconium, or other atoms substitutedfor one or more of the atoms not already contained in the parentframework.

The following listing of Embodiments is intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1. A crystalline microporous germanosilicate compositioncomprising a three dimensional framework having pores defined by 10- and14-membered rings. As should be apparent from the descriptions herein,these 10- and 14-membered rings comprise silicon-oxygen andgermanium-oxygen linkages and that 10- and 14-membered refer to thenumber of oxygen atoms in the respective rings.

Embodiment 2. A crystalline microporous germanosilicate composition,which exhibits at least one of:

(a) a powder X-ray diffraction (XRD) pattern exhibiting at least five ofthe characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2,18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2,26.01±0.2, and 26.68±0.2 degrees 2-θ;

(b) a powder X-ray powder diffraction (XRD) pattern substantially thesame as shown in FIG. 1(B) or 1(C); or

(c) unit cell parameters substantially equal to the following:

Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V(Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)

Embodiment 3. The crystalline microporous germanosilicate composition ofEmbodiment 1 or 2, which exhibits a powder X-ray diffraction (XRD)pattern exhibiting at least five of the characteristic peaks at6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2, 18.36±0.2, 18.63±0.2,20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2, 26.01±0.2, and 26.68±0.2degrees 2-θ. In separate Aspects of this Embodiment, the compositionexhibits six, seven, eight, nine, or ten of the characteristic peaks. Inother Aspects of this Embodiment, the composition contains 5, 6, 7, 8,9, 10, or more of the peaks identified in Table 3.

Embodiment 4. The crystalline microporous germanosilicate composition ofany one of Embodiments 1 to 3 which exhibits a powder X-ray diffraction(XRD) pattern substantially the same as shown in FIG. 1(A), 1(B), or1(C).

Embodiment 5. The crystalline microporous germanosilicate composition ofany one of Embodiments 1 to 4 which exhibits unit cell parameterssubstantially equal to the following at:

Space group Cmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V(Å³) 3896.6(1) Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1)

Embodiment 6. The crystalline microporous germanosilicate composition ofEmbodiment 2, exhibiting at least two of (a), (b), or (c).

Embodiment 7. The crystalline microporous germanosilicate composition ofany one of Embodiments 1 to 6, wherein the channel dimensions of the 10-and 14-membered rings are 6.2×4.5 Å and 9.1×7.2 Å, respectively.

Embodiment 8. The crystalline microporous germanosilicate composition ofany one of Embodiments 1 to 7, having a ratio of Si:Ge atoms in a rangeof from 2:1 to 16:1.

Embodiment 9. The crystalline microporous germanosilicate composition ofany one of claims 1 to 8, that is substantially free of an organicstructure-directing agent (OSDA)

Embodiment 10. The crystalline microporous germanosilicate compositionof any one of Embodiments 1 to 8, further comprising at least onesubstituted benzyl-imidazolium organic structure-directing agent (OSDA).

Embodiment 11. The crystalline microporous germanosilicate compositionof Embodiment 10, wherein the at least one substitutedbenzyl-imidazolium organic structure-directing agent has a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C₁₋₃ alkyl.

Embodiment 12. The crystalline microporous germanosilicate compositionof Embodiment 11, wherein the at least one substitutedbenzyl-imidazolium organic structure-directing agent has a structure:

Embodiment 13. An aqueous composition comprising:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one substituted benzyl-imidazolium organicstructure-directing agent (OSDA) having a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C1-3 alkyl; and

(e) a crystalline microporous germanosilicate composition of any one ofEmbodiments 1 to 12.

Embodiment 14. The aqueous composition of Embodiment 13, wherein:

(a) the source of silicon oxide comprises tetraethyl orthosilicate(TEOS); or

(b) the source of germanium oxide comprises GeO2, or a hydratedderivative thereof; or

(c) both (a) and (b).

Embodiment 15. The aqueous composition of Embodiment 13 or 14, whereinthe mineralizing agent comprises:

(a) a fluoride source comprising hydrofluoric acid, or a salt orderivative thereof;

(b) an alkali metal hydroxide or alkaline earth metal hydroxide, orcombination thereof.

Embodiment 16. The aqueous composition of any one of Embodiments 13 to15, wherein the at least one substituted benzyl-imidazolium organicstructure-directing agent has a structure:

Embodiment 17. The aqueous composition of any one of Embodiments 13 to16, wherein the crystalline microporous germanosilicate has occludedwithin its pores at least one of the substituted benzyl-imidazoliumorganic structure-directing agents. In other Aspects of this Embodiment,the crystalline microporous germanosilicate is substantially free of anyorganic structuring agent.

Embodiment 18. The aqueous composition of any one of Embodiments 13 to17, wherein the composition is a suspension or a gel.

Embodiment 19. A method comprising hydrothermally treating an aqueouscomposition comprising:

(a) a source of silicon oxide

(b) a source of germanium oxide;

(c) a mineralizing agent;

(d) at least one substituted benzyl-imidazolium organicstructure-directing agent (OSDA) having a structure:

but not

wherein m and n are independently 1, 2, or 3, and R¹, R², and R³ areindependently at each occurrence C1-3 alkyl, under conditions effectiveto crystallize a crystalline microporous germanosilicate composition ofany one of Embodiments 1 to 8.

Embodiment 20. The method of Embodiment 19, wherein:

(a) the source of silicon oxide comprises tetraethyl orthosilicate(TEOS), or any of the sources of silicon oxide otherwise cited herein;or

(b) the source of germanium oxide comprises GeO₂, or a hydratedderivative thereof or (c) both (a) and (b).

Embodiment 21. The method of Embodiment 19 or 20, wherein the source ofsilicon oxide and the source of germanium oxide are present in a molarratio in a range of from about 2:1 to about 8:1.

Embodiment 22. The method of any one of Embodiments 19 to 21, whereinthe mineralizing agent comprises:

(a) a fluoride source comprising hydrofluoric acid, or a salt orderivative thereof or

(b) a source of hydroxide; or

(c) both a source of fluoride and hydroxide.

Embodiment 23. The method of any one of Embodiments 19 to 22, whereinthe mineralizing agent comprises hydrofluoric acid or ammonium fluoride.

Embodiment 24. The method of any one of Embodiments 19 to 22, whereinthe mineralizing agent comprises an alkali metal hydroxide or alkalineearth metal hydroxide, or combination thereof.

Embodiment 25. The method of any one of Embodiments 19 to 24, whereinthe at least one substituted benzyl-imidazolium organicstructure-directing agent has a structure:

Embodiment 26. The method of any one of Embodiments 19 to 25, whereinthe crystalline microporous germanosilicate has occluded within itspores at least one of the substituted benzyl-imidazolium organicstructure-directing agents.

Embodiment 27. The method of any one of Embodiments 19 to 25, whereinthe crystalline microporous germanosilicate is substantially free ofoccluded substituted benzyl-imidazolium organic structure-directingagents.

Embodiment 28. The method of any one of Embodiments 19 to 27, whereinthe composition is a suspension or a gel.

Embodiment 29. The method of any one of claims 19 to 28, whereineffective crystallization conditions include a temperature of from about140° C. to about 180° C., and a time of from about 4 days to about 4-6weeks.

Embodiment 30. The method of any one of Embodiments 19 to 29, furthercomprising isolating a product crystalline microporous germanosilicatesolid which exhibits of at least one of the characteristics describedfor any one of Embodiments 1 to 8.

Embodiment 31. The method of Embodiment 30, further comprising:

(a) heating the isolated product crystalline microporous germanosilicatesolid at a temperature in a range of from about 250° C. to about 450°C.; or

(b) contacting the isolated product crystalline microporousgermanosilicate solid with ozone or other oxidizing agent at atemperature in a range of 25° C. to 200° C.;

for a time sufficient to form a dehydrated or an OSDA-depleted product.

Embodiment 32. The method of Embodiment 31, further comprising:

(a) treating the dehydrated or OSDA-depleted product with an aqueousalkali, alkaline earth, transition metal, rare earth metal, ammonium oralkylammonium salt; and/or

(b) treating the dehydrated or OSDA-depleted product with at least onetype of transition metal or transition metal oxide.

Embodiment 33. The method of any one of Embodiments 30 to 32, furthercomprising calcining the isolated crystalline microporous solid in air atemperature in a range of from about 500° C. to about 1200° C.

Embodiment 34. A crystalline microporous germanosilicate compositionprepared according to a method of any one of Embodiments 19 to 33.

Embodiment 35. A process for affecting an organic transformation, theprocess comprising:

(a) carbonylating DME with CO at low temperatures;

(b) reducing NOx with methane:

(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;

(d) dewaxing a hydrocarbon feedstock;

(d) converting paraffins to aromatics:

(e) isomerizing or disproportionating an aromatic feedstock;

(f) alkylating an aromatic hydrocarbon;

(g) oligomerizing an alkene;

(h) aminating a lower alcohol;

(i) separating and sorbing a lower alkane from a hydrocarbon feedstock;

(j) isomerizing an olefin;

(k) producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon;

(l) reforming a hydrocarbon

(m) converting a lower alcohol or other oxygenated hydrocarbon toproduce an olefin products (including MTO);

(n) epoxiding olefins with hydrogen peroxide;

(o) reducing the content of an oxide of nitrogen contained in a gasstream in the presence of oxygen;

(p) separating nitrogen from a nitrogen-containing gas mixture;

(q) converting synthesis gas containing hydrogen and carbon monoxide toa hydrocarbon stream; or

(r) reducing the concentration of an organic halide in an initialhydrocarbon product;

by contacting the respective feedstock with the a catalyst comprisingthe crystalline microporous solid of any one of claim 1 to 9 or 34 orprepared according to a method of any one of claims 19 to 33, underconditions sufficient to affect the named transformation.

Embodiment 36. The process of Embodiment 36 comprising:

(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon;

(d) dewaxing a hydrocarbon feedstock;

(d) converting paraffins to aromatics:

(e) isomerizing or disproportionating an aromatic feedstock;

(f) alkylating an aromatic hydrocarbon;

(g) oligomerizing an alkene;

(i) separating and sorbing a lower alkane from a hydrocarbon feedstock;

(j) isomerizing an olefin;

(k) producing a higher molecular weight hydrocarbon from lower molecularweight hydrocarbon; or

(l) reforming a hydrocarbon.

Embodiment 37. The process of Embodiment 35 comprising convertingsynthesis gas containing hydrogen and carbon monoxide to a hydrocarbonstream using a catalyst comprising the crystalline microporousgermanosilicate composition and a Fischer-Tropsch catalyst (see U.S.Pat. No. 9,278,344).

Embodiment 38. The process of Embodiment 35 comprising reducing theconcentration of an organic halide in an initial hydrocarbon product,the initial hydrocarbon product containing an undesirable level of theorganic halide, the process comprising contacting at least a portion ofthe initial hydrocarbon product with a composition comprising thecrystalline microporous germanosilicate composition, under organichalide absorption conditions to reduce the halogen concentration in thehydrocarbon. (see U.S. Pat. No. 8,105,481).

Embodiment 39. A process of trapping low molecular weight hydrocarbonsfrom an incoming gas stream comprising passing the gas stream across orthrough a composition comprising the crystalline microporousgermanosilicate composition of any one of claim 1 to 9 or 34 or preparedaccording to a method of any one of claims 19 to 33, so as to provide anoutgoing gas stream having a reduced concentration of low molecularweight hydrocarbons relative to the incoming gas stream.

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1 Materials and Methods

Unless otherwise noted, all reagents were purchased from commercialsources and were used as received. Unless otherwise noted all, reactionswere conducted in flame-dried glassware under an atmosphere of argon.Hydroxide ion exchanges were performed using OH-formstyrene-divinylbenzene (DVB)-matrix ion exchange resin (DOWEX™ MARATHON™A) with an exchange capacity of 1 meq/mL. Titrations were performedusing a Mettler-Toledo DL22 autotitrator using 0.01 M HCl as thetitrant. All liquid NMR spectra were recorded with a 500 MHz VarianSpectrometer. Liquid NMR spectra were recorded on Varian Mercuryspectrometers.

All powder x-ray diffraction characterization were conducted on a RigakuMiniFlex II diffractometer with Cu Kα radiation.

Solid-state NMR (¹³C and ²⁹Si) spectra were obtained using a BrukerDSX-500 spectrometer (11.7 T) and a Bruker 4 mm MAS probe. The spectraloperating frequencies were 500 MHz, 125.7 MHz, and 99.4 MHz for ¹H, ¹³C,and ²⁹Si nuclei, respectively. Spectra were referenced to externalstandards as follows: tetramethylsilane (TMS) for ¹H and ²⁹Si andadamantane for ¹³C as a secondary external standard relative totetramethylsilane. Samples were spun at 14 kHz for ¹H NMR and 8 kHz for¹³C and ²⁹Si MAS and CPMAS NMR experiments.

Thermogravimetric analysis (TGA) was performed on a Perkin Elmer STA6000 with a ramp of 10° C.min⁻¹ to 900° C. under air atmosphere. Samples(0.01-0.06 g) were placed in aluminum crucible and heated at 1 K/min ina flowing stream (0.667 cm³/s) comprised of 50% air (Air Liquide,breathing grade) and 50% argon (Air Liquide, UHP).

SEM analyses were performed on a ZEISS 1550 VP FESEM, equipped with anOxford X-Max SDD X-ray Energy Dispersive Spectrometer (EDS) system fordetermining the Si/Al ratios of the samples.

Example 2 Synthesis of the Organic Structuring Agents

A series of six monoquatemary (“monoquat”) and three diquaternary(“diquat”) organic structure-directing agents (OSDAs) were studied.These six monoquats and three diquats, along with their numericaldesignations, can be found in Tables 1A, 1B, and 1C:

TABLE1A Monoquat benzyl-imidazolium cations studied in this workBenzyl-imidazolium (1)

Benzyl-imidazolium (2)

Benzyl-imidazolium (3)

TABLE1B Monoquat benzyl-imidazolium cations studied in this workBenzyl-imidazolium (4)

Benzyl-imidazolium (5)

Benzyl-imidazolium (6)

TABLE1C Diquat benzyl-diimidazolium dications studied in this workBenzyl-diimidazolium (7)

Benzyl-diimidazolium (8)

Benzyl-diimidazolium (9)

These were prepared as follows. Unless stated otherwise, reactions wereconducted in flame-dried glassware under an atmosphere of argon.

Example 2.1

Preparation of 1,2-Dimethyl-3-(2-methyl-benzyl)imidazol-1-ium chloride(“Benzyl-imidazolium (1)” or “OSDA 1”). A 500 mL flask was charged with1,2-dimethylimidazole (7.73 grams, 55.0 mmols), 2-methylbenzyl chloride(7.73 grams, 60.5 mmols) and toluene (100 mL). The flask was fitted witha reflux condenser and heated to reflux for 15 hours. Reaction wascooled to 25° C. and resulting solids were filtered and washed withethyl acetate (3×20 mL) to give a white solid (11.84 grams, 91% yield).¹H NMR (500 MHz, CD₃OD): δ 7.37-7.33 (m, 2H), 7.31 (d, J=5.0 Hz, 1H),7.30-7.26 (m, 1H), 7.02 (d, J=5.0 Hz, 1H) 5.45 (s, 2H), 3.92 (s, 3H),2.67 (s, 3H), 2.38 (s, 3H). ¹³C NMR (126 MHz, CD₃OD) δ 145.08, 136.40,131.36, 130.69, 128.81, 127.56, 126.47, 122.44, 120.88, 49.59, 34.15,17.66, 8.35.

Example 2.2

Preparation of 1,2-Dimethyl-3-(3-methyl-benzyl)imidazol-1-ium chloride(“Benzyl-imidazolium (2)” or “OSDA 2”). This OSDA was prepared as inExample 2.1, except that 3-methylbenzyl chloride was used instead of2-methylbenzyl chloride. The reaction yielded a beige solid (22.65grams, 87% yield). ¹H NMR (500 MHz, CD₃OD): δ 7.55 (s, 2H), 7.34 (dd,J=10.0, 5.0, 1H), 7.25 (d, J=10.0, 1H), 7.20 (s, 1H), 7.14 (d, J=5.0,1H), 5.40 (s, 2H), 3.88 (s, 3H), 2.67 (s, 3H), 2.39(s, 3H). ¹³C NMR(125.7 MHz, CD₃OD) δ 144.8, 139.1, 133.7, 129.3, 128.9, 128.1, 124.6,122.4, 121.2, 51.3, 34.1, 19.9, 8.4.

Example 2.3

Preparation of 1,2-Dimethyl-3-(3-methylbenzyl)imidazolium hydroxide(“Benzyl-imidazolium (2)” or “OSDA 2”). This OSDA was prepared accordingto the method of Example 2.2, except that the obtained chloride salt wasrepeatedly washed with 4 L of diethyl ether and dried under vacuum for12 hours. The chloride anions were exchanged with hydroxyl anions usingOH-form styrene-divinylbenzene (DVB)-matrix ion exchange resin (DOWEX™MARATHON™ A). ¹H NMR (500 MHz, CDCl₃): δ 7.79 (d, 1H), 7.58 (d, 1H),7.29 (m, 1H), 7.19 (m, 1H), 7.11 (m, 1H), 7.10 (m, 1H), 5.49 (s, 2H),4.03 (s, 3H), 2.81 (s, 3H), 2.37 (s, 3H). ¹³C NMR (125.7 MHz, CDCl₃): δ144.29, 139.37, 132.79, 129.92, 129.29, 128.60, 125.10, 122.96, 121.73,52.46, 35.90, 21.36, 10.90.

Example 2.4

Preparation of 1,2-Dimethyl-3-(4-methyl-benzyl) imidazol-1-ium hydroxide(“Benzyl-imidazolium (3)” or “OSDA 3”). This OSDA was prepared accordingto the method of Example 2.1, except that 4-methylbenzyl chloride wasused instead of 2-methylbenzyl chloride. The reaction yielded a whitesolid (24.10 grams, 92% yield). The chloride anions were exchanged withhydroxyl anions using OH-form styrene-divinylbenzene (DVB)-matrix ionexchange resin (DOWEX™ MARATHON™ A). ¹H NMR (500 MHz, CD₃OD): δ7.54-7.53 (m, 2H), 7.28 (d, J=5.0, 2H), 7.28 (d, J=5.0, 2H), 5.34(s,2H), 3.87 (s, 3H), 2.67 (s, 3H), 2.39(s, 3H). ¹³C NMR (125.7 MHz, CD₃OD)δ 144.8, 138.8, 130.7, 129.5, 127.6, 122.4, 121.1, 51.2, 34.1, 19.7,8.4.

Example 2.5

Preparation of 1-methyl-3-(3-methylbenzyl)imidazolium hydroxide(“Benzyl-imidazolium (4)” or “OSDA 4”). 1-Methylimidazole (14.4 g, 150mmol) was dissolved in 300 ml of toluene and heated up to 45° C. Whilevigorously stirring, 3-methylbenzyl chloride (21.1 g, 150 mmol) wasadded dropwise. After 30 min of additional stirring, the temperature wasincreased to 105° C. and the reaction proceeded for 24 hours. Afterthat, the reaction mixture was cooled in a dry ice bath since thisimidazolium salt exists as a liquid salt at the room temperature in itschloride form. A cold filtration was performed to isolate the product insolid form. The obtained chloride salt was repeatedly washed with 4 L ofcold diethyl ether and dried under vacuum for 12 hours. The chlorideanions were exchanged with hydroxyl anions using OH-formstyrene-divinylbenzene (DVB)-matrix ion exchange resin (DOWEX™ MARATHON™A). ¹H NMR (500 MHz, CDCl₃): δ 10.54 (s, 1H), 7.64 (t, 1H), 7.32 (m,1H), 7.14 (m, 3H), 7.05 (m, 1H), 5.42 (s, 2H), 3.97 (s, 3H), 2.22 (s,3H). ¹³C NMR (125.7 MHz, CDCl₃): δ 139.14, 137.42, 133.02, 130.04,129.28, 129.12, 125.77, 123.92, 121.78, 53.07, 36.46, 21.21.

Example 2.6

Preparation of 1,2-Dimethyl-3-(3,5-dimethylbenzyl)imidazolium hydroxide(“Benzyl-imidazolium (5)” or “OSDA 5”). 1,2-Dimethylimidazole (12.3 g,150 mmol) was dissolved in 300 ml of toluene in an ice bath. Whilevigorously stirring, 3,5-dimethylbenzyl bromide (29.9 g, 150 mmol) wasadded. After 30 min of additional stirring, the temperature was slowlyincreased to 105° C. and the reaction proceeded for 15 hours, afterwhich the reaction mixture was cooled and filtered. The obtainedchloride salt was repeatedly washed with 4 L of diethyl ether and driedunder vacuum for 12 hours. The chloride anions were exchanged withhydroxyl anions using OH-form ion exchange resin. ¹H NMR (500 MHz,CDCl₃): δ 7.77 (d, 1H), 7.49 (d, 1H), 6.99 (m, 1H), 6.89 (m, 2H), 5.41(s, 2H), 4.03 (s, 3H), 3.19 (s, 3H), 2.31 (s, 6H). ¹³C NMR (125.7 MHz,CDCl₃): δ 144.29, 139.19, 132.55, 130.81, 125.71, 122.92, 121.61, 52.57,36.19, 21.23, 11.38.

Example 2.7

Preparation of 1-Methyl-3-(3,5-dimethylbenzyl)imidazolium hydroxide(“Benzyl-imidazolium (6)” or “OSDA 6”). This OSDA was prepared accordingto the method of Example 2.6 using 1-methylimidazole and3,5-dimethylbenzyl bromide. The obtained chloride salt was repeatedlywashed with 4 L of diethyl ether and dried under vacuum for 12 hours.The chloride anions were exchanged with hydroxyl anions using OH-formion exchange resin. ¹H NMR (500 MHz, CDCl₃): δ 10.46 (td, 1H), 7.53 (t,1H), 7.27 (d, 1H), 7.00 (dm, 3H), 5.44 (s, 2H), 4.09 (s, 3H), 2.28 (s,6H). ¹³C NMR (125.7 MHz, CDCl₃): δ 139.23, 137.34, 132.55, 131.17,126.59, 123.65, 121.71, 53.44, 36.78, 21.18.

Example 2.8

Preparation of (“Benzyl-diimidazolium (7)” or “OSDA 7”). A 500 mL flaskwas charged with 1,2-dimethyl imidazole (16.0 g, 166.7 mmol),α,α′-dichloro-o-xylene (20.0 g, 75.8 mmol) and ethanol (300 mL). Theflask was fitted with a reflux condenser and heated to reflux for 15 h.The reaction was cooled to 0° C. and resulting solids were filtered andwashed with ethyl acetate (3×50 mL) to give (27.10 g, 78% yield) a whitesolid. ¹H NMR (500 MHz, CD₃OD): δ 7.58 (d, J=2.0, 2H), 7.45 (dd, J=3.5,2.5 2H), 7.43 (d, J=2.0, 2H), 7.02 (dd, J=3.5, 2.5 2H), 5.64 (s, 4H),3.91 (s, 6H), 2.68 (s, 6H). ¹³C NMR (126 MHz, CD₃OD): 147.04, 133.03,130.76, 129.02, 124.21, 122.49, 50.19, 35.86, 10.36.

Example 2.9

Preparation of (“Benzyl-diimidazolium (8)” or “OSDA 8”). The reactionwas carried out as in Example 2.8, except the α,α dibromo-m-xylene wasused (82% yield). ¹H NMR (500 MHz, CD₃OD) 7.53-7.47 (m, 5H), 7.44-7.42(m, 1H), 7.35-7.33 (m, 2H), 5.45 (s, 4H), 3.86 (s, 6H), 2.65 (s, 6H).¹³C NMR (126 MHz): 145.05, 135.08, 129.94, 127.95, 127.29, 122.57,121.13, 50.82, 34.27, 8.70.

Example 2.10

Preparation of (“Benzyl-diimidazolium (9)” or “OSDA 9”). This time thereaction as in Example 2.8, but using α,α dichloro-p-xylene. The producthad a yield of 78%. ¹H NMR (500 MHz, CD₃OD) 7.52 (d, J=2.5, 2H), 7.51(d, J=2.5 2H), 7.40 (s, 4H), 5.43 (s, 4H), 3.84 (s, 6H), 2.63 (s, 6H).¹³C NMR (126 MHz, CD₃OD): 146.44, 136.05, 129.88, 123.98, 122.56, 52.16,35.62, 9.94.

Example 3 Syntheses of Crystalline Materials

All reactions were performed in 23 mL Teflon-lined stainless steelautoclaves (Parr instruments). Reactions were performed eitherstatically or tumbled at approximately 40 rpm using spits built intoconvection ovens. Silicon source was tetraethyl orthosilicate (99.9%Si(OCH₂CH₃)₄, Strem). Germanium source was germanium oxide (99.99% GeO₂,Strem).

Gels for germanosilicate reactions were prepared by adding germaniumoxide to a solution of the organic structure-directing agent in waterdirectly into the 23 mL Teflon liner. This mixture is stirred at 25° C.for 5 minutes, or until germanium oxide has dissolved into the solution.Tetraethyl orthosilicate was then added, reaction vessel is capped, andstirred for an additional 12 hours to hydrolyze the tetraethylorthosilicate. The reaction vessel was then uncapped and a stream of airwas blown over the gel, while it was mechanically stirred, until therequired excess of water and hydrolyzed ethanol has been evaporated. Incertain cases, the gel was put under vacuum to remove small amounts ofresidual water, when evaporation failed to remove the required amount ofwater. Hydrofluoric acid was then added in a dropwise fashion to the geland the Teflon liner was sealed into the stainless steel autoclave andput into the oven. The reactors were opened every 6-7 days to assessreaction progress. After homogenizing, a small sample was successfullywashed with deionized H₂O (2×10 mL) and acetone:methanol (1:1, 3×10 mL)and the XRD pattern was inspected. All reactions were monitored for atleast 1 month.

The variable ratios used for the reactions were 1.0 SiO₂/xGeO₂ wherex=0.50 and lower/0.50 OSDA as OH-/0.50 HF/5 H₂O. In the products thereis a slight enrichment of Si/Ge over the starting ratio and in theCIT-13 product where reaction Si/Ge=4, the product has a value closer to5 (by EDX measurements).

Example 3.1

Synthesis of Germanosilicate CIT-13 in Fluoride Media. The protocol forthe synthesis of the germanosilicate microporous crystals has beenpreviously reported. In this work, the gel composition was x/(x+1)SiO₂:1/(x+1) GeO₂:0.5-0.75 (OSDA)+OH-:0.5-0.75 HF:5-15 H₂O where x isthe Si/Ge molar ratio of the gel. A desired amount of germanium (IV)oxide (GeO₂) was dissolved in a desired amount of OSDA aqueous solutionand tetraethyl orthosilicate (TEOS) in a 23 ml PTFE liner (ParrInstrument). The mixture was stirred for 12 hours in order to hydrolyzeall TEOS, and dried under a continuous air flow to evaporate excesswater and ethanol until the gel became very viscous. The equivalentamount of concentrated hydrofluoric acid (HF, 48 wt %) was addeddropwise and thoroughly mixed using a PTFE spatula. After the HF mixing,the mixture became powdery. After an additional 2 days of drying, adesired amount of distilled water was added and mixed thoroughly. ThePTFE liner containing the mixture was firmly clad with a Parr stillreactor and put in a static convection oven. The crystallizationtemperature was typically 160° C., but other temperature in a range from140° C. to 175° C. could be chosen. The crystallization had beenmonitored for at least 1 month. The resultant CIT-13 crystal wascarefully washed with distilled water, methanol and acetone, and driedin a 70° C. convection oven before being characterized.

Example 3.2

Synthesis of Germanosilicate CIT-13 using Ammonium Fluoride (NH₄F). Thegel composition for the NH₄F-protocol was the same as the HF-protocoldescribed above, except for the fact that a molar-equivalent amount ofNH₄F was used instead of HF. Desired amounts of GeO₂ and NH₄F weredissolved in OSDA aqueous solution and TEOS in a 23 ml PTFE liner. Themixture was stirred for 12 hours in order to hydrolyze all TEOS, anddried under a continuous air flow to evaporate excess water, ammonia andethanol until the gel became completely powdery. And then, water wasadded to a desired level. The PTFE liner containing the mixture wasfirmly clad with a Parr still reactor and put in a static convectionoven at 160° C. The rest of the protocol is the same as above.

Example 3.3

Synthesis of Germanosilicate IM-12 (UTL) in Hydroxide Media. Thegermanosilicate IM-12 of the UTL framework was synthesized to make adirect comparison with CIT-13. A spiro-quaternary ammonium,(6R,10S)-6,10-dimethyl-5-azaspiro[4.5]decanium hydroxide, was used asthe OSDA for the synthesis of IM-12. This OSDA was prepared according tothe protocol reported by Paillaud et al and other researching groups.The IM-12 germanosilicate was solvothermally synthesized using a hydroxy(OH—)-medium. The gel composition used in this work was 0.667 SiO₂:0.333GeO₂:0.25 (OSDA)+OH-:30 H₂O. The gel mixture was prepared by dispersingdesired amounts of silica (Cab-o-Sil®) and GeO2 in (OSDA⁺)OH⁻ solutionand, the water content was adjusted by simply adding an equivalentamount of distilled water. The crystallization was performed at 175° C.for 14 day in a 23 ml Parr reactor. The rinsing step of the preparedIM-12 crystal was the same as the procedures for CIT-13 described above.

[From P-1] Example 3.4 Screening Reactions Using MonoquatBenzyl-Imidazolium Cations (1), (2), and (3)

These monoquats were studied in germanosilicate, fluoride-mediatedreactions, with the composition of: (1-x) Si:x Ge:0.5 HF:0.5 ROH:5.0 H₂Owith all reactions being performed statically at 160° C. Results of thesyntheses are given in Table 2.

TABLE 2 Synthesis results using benzyl-imidazolium cations (1), (2), and(3) OSDA Si/Ge = 2 Si/Ge = 4 Si/Ge = 8 Si/Ge = 16 1 IWS CIT-13 LTA/Amorphous Amorphous 2 CIT-13 CIT-13 CIT-13 CIT-13 3 BEC/LTA BEC/LTA LTALTA

Table 2 shows the products obtained with these three monoquats. Theproduct denoted CIT-13 was obtained at a range of Si/Ge ratios and withOSDA 1 and 2. A representative powder XRD pattern of both the as-madeand calcined material is shown in FIGS. 1(A-C). This powder pattern hasnot been known before and represents a new material, designated hereinas CIT-13. It could be produced reproducibly and does not match anyknown material (search done using Jade database). In the as-madematerials there was some variably in peak intensities between materials.This is commonly found in as-made materials and is attributed to theinfluence of the organic and OSDA. There were also impurity phasescommonly encountered in these syntheses, so once a pure-phase materialwas found seeding was used in all subsequent syntheses.

The characteristic 2-theta peaks for the CIT-13 material are provided inTable 3.

TABLE 3 Powder XRD peaks for CIT-13; estimated variances in 2-θ are±0.2°. Actual intensities often vary from theoretical values 2-θ,Theoretical No. deg Intensity Comment 1 6.45 100 Very strong (200) peak,from interlayer spacing 2 7.18 96.06 Very strong (110) 3 8.56 13.98Almost invisible in practice 4 10.73 9.51 Almost invisible in practice 511.18 15.42 Almost invisible in practice 6 12.85 4.84 Generally 5-10times stronger than theoretical 7 18.26 18.20 Indistinguishable 8 18.3611.11 in practice 9 18.63 12.78 — 10 19.60 4.30 — 11 20.78 16.13 — 1221.55 9.61 — 13 23.36 9.34 — 14 24.55 8.37 — 15 25.7 4.53 — 16 25.304.47 — 17 25.87 3.58 — 18 26.01 4.93 Generally 5-10 times stronger thantheoretical 19 26.68 14.48 — 20 33.99 3.74 —

Example 3.5

Screening Reactions using Monoquat Benzyl-Imidazolium Cations (2), (4),(5), and (6). An expanded set of experiments are described in Table 4.

TABLE 4 Summary of synthesis conditions tested in this study. All ratiosare in molar ratios. All reactions at 160° C. (SDA)OH/T Si/ and Ge H₂O/THF/T Time Major Pu- OSDA gel gel * (gel) * Seed? (days) Phase rity 2 415 0.5 Y 28 CIT-13  >95% 2 4 15 0.5 N 35 CIT-13  >95% 2 2 10 0.5 N 14CIT-13  >95% 2 3 10 0.5 N 14 CIT-13 ~100% 2 4 10 0.5 Y 7 CIT-13 ~100% 24 10 0.5 N 21 CIT-13 ~100% 2 8 10 0.5 N 21 CIT-13 Major 2 16 10 0.5 N 35CIT-13 Major 2 4 7.5 0.5 Y 14 CIT-13  >95% 2 4 7.5 0.5 N 14 CIT-13 ~100%2 4 5 0.5 Y 21 CIT-13  >95% 2 4 10 0.5 N 28 CIT-13 ~100% 2 4 10 0.5 N 28CIT-13 ~100% 2 4 10 0.5 N 7 CIT-13 ~100% 2 4 10 0.625 Y 14 CIT-13  >95%2 4 10 0.625 N 14 CIT-13  >95% 2 4 10 0.75 Y 14 CIT-13 Major 2 4 10 0.75N 14 CIT-13 Major 4 2 10 0.5 N 14 CIT-13/ Major MFI 4 4 10 0.5 N 14CIT-13/ Major MFI 4 8 10 0.5 N 14 MFI — 4 16 10 0.5 N 28 MFI — 4 50 100.5 N 28 MFI — 5 2 10 0.5 N 21 CIT-13 Major 5 4 10 0.5 N 21 CIT-13 Major5 8 10 0.5 N 21 CIT-13 Major 5 16 10 0.5 N 56 CIT-13 Major 5 50 10 0.5 N56 Amor- — phous 6 2 10 0.5 N 7 CIT-13 ~100% 6 4 10 0.5 N 7 CIT-13 ~100%6 8 10 0.5 N 14 CIT-13  >95% 6 16 10 0.5 N 21 CIT-13  >95% 6 50 10 0.5 N49 Amor- — phous * T refers to the total number of Si and Ge atoms

[From Boal] Example 3.6

Screening Reactions using Di-quat Benzyl-Imidazolium Cations (7), (8),and (9). Table 5 shows the ratios explored for Si and Ge in the initialmolecular sieve synthesis, and the resulting materials obtained when thediquaternary OSDAs were each used in a synthesis. It was observed thatas the relative proportion of Ge diminished, the tendency to make *BEAwith all three diquaternary OSDAs increased, consistent with previousreports that the very large diquaternary OSDA (often having parasubstitution relative to a central ring component) could be used toobtain very high silica *BEA phases. The *BEA is a multidimensional (3D)large pore zeolite but not so rich in 4-rings, indicative of a minorcontribution of Ge.

TABLE 5 Synthesis results of Diquat OSDAs (7)-(9) OSDA Si/Ge = 2 Si/Ge =4 Si/Ge = 8 Si/Ge = 16 7 layered layered *BEA *BEA 8 IWS IWS/*BEA *BEA*BEA 9 BEC BEC/*BEA *BEA/BEC *BEA

Example 5

Analysis—Influences of crystallization parameters Using abenzylimidazolium-derived OSDA (OSDA 2), the crystallization conditionsfor CIT-13 were tested systematically and kinetically at various levelsof silicon-to-germanium (Si/Ge) ratios of the gel, water contents,seeding material, amounts of SDA+OH—/HF used and crystallizationtemperatures. The structures of OSDAs investigated in this study weredisplayed in Tables 1A-C, and some of the tested conditions aresummarized in Table 4. The purity was qualitatively determined based onthe resultant XRD profiles.

The reference crystallization condition suggested by this work thatproduces the-highest-quality CIT-13 crystal reproducibly was determinedto be 0.8 SiO₂:0.2 GeO₂:0.5 (OSDA 1)+OH-:0.5 HF:10 H₂O at 160° C. Withthis set of crystallization parameters, an impurity-free CIT-13 samplecould be obtained after 14-21 days of crystallization time. Themorphology of the CIT-13 crystals very resembled that of UTL-frameworkmaterials, indicating that these two frameworks having similar 2D-portalsystems are closely related. (See FIG. 2(C-D)) The other crystallizationconditions varied from this reference condition. XRD profiles fromseveral conditions that give better CIT-13 crystals than the other weredisplayed in FIG. 3.

The Si/Ge ratio of gel was controlled from 2 to 16, and kineticallystudied using XRD. (FIG. 4). The higher Si/Ge ratio of gel led to thefaster crystallization of CIT-13 and the higher germanium content in thecrystals. When the gel Si/Ge ratios were 2, 3 and 4, the Si/Ge atomicratios determined using EDS were 3.84±0.59, 4.72±0.55 and 5.73±0.89,respectively. The resultant CIT-13 crystals typically showed Si/Geatomic ratio higher than that of the parent gels, and this fact was alsotrue in case of the UTL sample. (FIG. 5) The amount of water in thesystems also affected the crystallization process of CIT-13. It wasalready shown that a gel of a low water content (H₂O/(Si+Ge)=5) alsocrystallized into CIT-13 in the previous work.1 In this work, threecases of higher water levels (H₂O/(Si+Ge)=7.5, 10 and 15) were testedand all of them were turned out to result in faster processes and bettercrystallinities than the cases of H₂O/(Si+Ge)=5. As shown in Table 4 andFIG. 6, CIT-13 was crystallized with acceptably high purities in thisrange of water contents, but the cases of H₂O/(Si+Ge)=7.5 and 10 wereclose to the optimal condition in respect of purity and crystallizationrate. The effect of the concentration of OSDA in the gel on the CIT-13crystallization was also studied. (FIG. 7) The amount of HF was alsochanged molar-equivalently considering the neutralization process. Thecases of OSDA/(Si+Ge)=0.5 and 0.625 gave relatively pure CIT-13 crystal,but some discernable impurity diffraction peaks were observed when theOSDA-to-T-atom ratio became higher than 0.75, implying that a differentmode of self-assembly of OSDA molecules that directs other phasehappened. Unfortunately, this phase could not be identified due tolittle available information.

With the reference gel composition, the influence of temperature on thecrystallization process of CIT-13 was also studied. As illustrated inFIG. 3, pure CIT-13 was synthesized at all studied temperatures: 140,150, 160 and 175° C. The crystallization was faster at highertemperature; at 175° C., CIT-13 was purely synthesized within 1 weekeven without initial seeding, whereas at least 4 weeks were required at140 and 150° C. (FIG. 8) Furthermore, as shown in FIG. 9, an increasedcrystallization temperature resulted in bigger crystals, indicating thatthe crystallization process of CIT-13 is diffusion-controlled.

Example 6

Analysis—OSDAs and crystallization of CIT-13. The substitution positionof the methyl group on the benzene ring of OSDA molecule played animportant role in determining the resultant germanosilicate framework;ortho-, meta- and para-monomethyl-substituted benzylimidazoliumderivatives yielded IWS/impure CIT-13, pure CIT-13 and LTA framework,respectively. In this work, the crystallization processes of CIT-13 fromthree selected OSDAs (OSDA 4-6) that have one or two methyl groups onlyon the meta-positions were studied at various gel Si/Ge ratio from 2 to50, in addition to OSDA 2. The XRD profiles in FIGS. 10-12 indicate thatall of the four OSDAs structure-directed the crystallization ofmicroporous germanosilicate to CIT-13 frameworks. Therefore, it islikely that the meta-substitution of methyl group(s) on the OSDA-benzenering is an important precondition for CIT-13 production. Specifically,OSDA 2 and OSDA 6 yielded much purer CIT-13 than the others; thesyntheses using these two SDAs resulted in pure CIT-13 germanosilicatecrystals with negligible or none of impurity phases as shown in FIGS.10-11 and 13. OSDA 4 resulted in the mixture of CIT-13 and MFIframework. When the system was Ge-rich, CIT-13 took the majority, whileMFI was the major phase when the gel Si/Ge was high. (FIG. 10) OSDA 5also resulted in CIT-13, but one or more impurity phase(s) were observedat all tested gel Si/Ge ratios (FIG. 11).

The as-prepared CIT-13 products from OSDA 2 and OSDA 6 were closelyexamined using ¹³C NMR and TGA which were displayed in FIG. 14(A-B). Thepeaks from the solution-phase ¹³C NMR spectra of OSDA 2 and OSDA 6matched those from the solid-state ¹³C MAS NMR of as-prepared CIT-13germanosilicate incorporating each OSDA. (See FIG. 14(A)) Together withwell-defined CIT-13 XRD profiles from these OSDAs demonstrated above, itcan be concluded that these two different OSDA moleculesstructure-directed the same framework CIT-13 without being dissociatedduring the crystallization. The TGA curves of as-prepared CIT-13 shownin FIG. 14(B) manifest approximately 16.5% (OSDA 2) and 15.6% (OSDA 6)weight loss during the temperature ramping from room-temperature to 900°C. indicating that a unit cell (64 T atoms) of CIT-13 has four OSDAmolecules. Since the molecular weights of OSDA 2 and OSDA 6 are thesame, the small difference between the two weight loss values may be dueto difference crystal-Si/Ge ratios of the two independent samples. Avalue of ˜17% of OSDA weight loss was a reasonable value for amicroporous material having a 2-dimensional pore system ofperpendicularly intersecting 14 and 10 MR channels.

Example 4 Structure Analysis of As-Synthesized CIT-13

A sample of CIT-13 produced using the reference conditions was used forstructural analysis. The structure was solved from rotation electrondiffraction (RED) data using the zeolite-specific program FOCUS (S.Smeets, et al., J. Appl. Crystallogr., 2013, 46, 1017-1023). Rietveldrefinement was initiated in the space group Cmmm (a=13.77 Å, c=27.32 Å)using the coordinates of the structure for CIT-13 proposed previouslyand the program TOPAS (A. A. Coelho, TOPAS-ACADEMIC v5.0, in, 2012).

The refinement resulted in a good fit to the data with agreement valuesR₁=0.013 and R_(wp)=0.077 (R_(exp)=0.0015). The main differences seem toarise from an anisotropic peak shape that affects some of thereflections. The refinement yields a Si:Ge ratio of 5.63. The Ge islocated primarily on T7 in the d4r, about half of which is Ge. The totaloccupancy of the OSDAs refined to 0.103, giving a total of 3.26 OSDAmolecules per unit cell (out a possible total of 4). Only 2 F⁻ werefound, so the remaining difference in the charge to balance thepositively charged OSDA was expected to be made up by 1.26 OH⁻disordered in the channel system. (See FIG. 2)

TABLE 6 Crystallographic details for the structure refinement ofas-synthesized CIT-13. Sample CIT-13 Chemical|(C₁₃N₂)_(3.30)F₂|[Si_(54.34)Ge_(9.66)O₁₂₈] composition Space group Cmmma (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V (Å³) 3896.6(1) Z 8ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1) 2θ range (°) 2.0-46.0 R_(I) 0.0126R_(wp) 0.0773 R_(exp) 0.0015 Observations 16899 Reflections 1241Parameters 104 Geometric 62 (inorganic germanosilicate) restraints 38(OSDA)

TABLE 7 Selected bond lengths and angles (Å, °). T—O—T O—T—O T—O CIT-13min 138.3 107.8 1.55 max 180.0 113.8 1.63 avg 156.6 109.6 1.59Restraints used: T—O—T: 135 ± 10°; O—T—O: 109.5 ± 0.8°; T—O: 1.61 ± 0.01Å; w = 1/σ²

Example 7

Comparison between CIT-13 and UTL. Table 8 shows a comparison of thephysicochemical data related to the channel and pore systems of IM-12and CIT-13. The micropore volume found for IM-12 is consistent with thepreviously reported results. The micropore volume of CIT-13 was slightlysmaller than that of IM-12, which is consistent with the fact that theframework density for CIT-13 (16.41 T-atoms nm⁻³) is higher than that ofIM-12 (15.60 T-atoms nm⁻³). The physisorption isotherm of CIT-13 showedtwo distinct pore filling phenomena in the micropore adsorption region(FIG. 15B). It is possible that the first pore filling atp/p_(o)˜10-4-10-3 arose from the high eccentricity of the 10-ringchannels and the second one at p/p₀=10⁻² was as observed because theaverage occupancy of 0.8 could no longer be reached. Such an orderedarrangement is highly unlikely. However, it does show that an A layercould become a B layer very easily and that the OSDA would not fit atthe boundary between the two, thus creating a deficiency in the amountof OSDA incorporated into the structure.

TABLE 8 Comparison of channel and pore systems of IM-12 and CIT-13,calculated based on germanosilicated of the Si/Ge ratio characterizedusing EDS IM-12 CIT-13 Sample Si-to-Ge ratio 4.5 5.0 Space group C2/mCmmm (monoclinic) (orthorhombic) Framework Density (T-atoms per nm³)15.60 16.41 Material density Pure silica 1.56 1.64 (g/cm³)Germanosilicate 1.77 1.84 Channel dimension 14 (9.5 × 7.1 Å) 14 (9.1 ×7.2 Å) 12 (8.5 × 5.5 Å) 10 (6.2 × 4.5 Å) Micropore Theoreticallyavailable 0.376 0.352 volume t-plot method 0.177 0.182 (cm³/g)Saito-Foley 0.205 0.222

Although the OSDA molecule was disordered, it seemed that two OSDAmolecules adopted a supramolecular arrangement at the center of the14-ring, in carrying out their structure-directing effect. The imidazolerings of an OSDA pair are parallel to one another, with a centroiddistance of 3.54(1) Å. Each pair can adopt one of four differentsymmetry-related positions. The methylbenzyl groups on either end of anOSDA pair point into the 10-rings. The occupancy of the OSDA refines to0.8, and this allows neighboring OSDA pairs to adopt a differentorientation occasionally.

Example 7 Analysis—Structural Comparison Between CIT-13 and UTL

As mentioned above, the crystal structure of CIT-13 from an orthorhombicspace group Cmmm was very closely related to that of UTL belonging to amonoclinic space group C2/m. To directly make comparisons between thetwo structures experimentally, Argon physisorption isotherms and ²⁹Sisolid-state NMR spectra were obtained for both of the two frameworks.(FIG. 16). The CIT-13 sample characterized in this part was synthesizedfrom the reference condition. The crystal Si/Ge ratio checked using EDSof this CIT-13 was 5.0±0.5. For UTL, IM-12 was synthesized separatelyfrom a hydroxide-medium, and its Si/Ge ratio was determined to be4.5±0.3. All samples subjected to these structural studies were freshlycalcined before the measurements.

The argon cryogenic physical adsorption isotherms of CIT-13 and UTL wereobtained at 87 K. (see FIG. 15) The micropore volumes of CIT-13 and UTLobtained using the t-plot methods were 0.177 cm³/g and 0.182 cm³/g,respectively, the latter value being consistent with previously reportedresults. The smaller micropore volume of CIT-13 than that of UTL wasconsistent with the denser framework of CIT-13; the framework density ofUTL is 15.60 T-atoms nm⁻³, while that of CIT-13 is 16.41 T-atoms nm⁻³.These framework density values were computed from CIF files of the twoframeworks using an open topological analysis tool TOTOPOL (see M. D.Foster, et al., A Database of Hypothetical Zeolite Structures, availableat http://www.hypotheticalzeolites.net at the time of this writing). Thecalcined CIT-13 showed a two-step argon adsorption behavior at very lowpressure range, indicating that the adsorption behavior inside the10MR-channel is very different to that of the 14MR-channel in viewpointof the micropore-filling mechanism. This eccentricity was not observedin the UTL framework. The micropore volume characterized based on thet-plot method was 0.18-0.19 cm³/g. It is believed that the first porefilling at p/p₀˜10⁻⁴-10⁻³ was due to the highly eccentric 10MR channelsand the second one at p/p₀=10-2 is originated from the 14MR channels.The pore size distribution of CIT-13 according to the cylindricalSaito-Foley (SF) model shown in FIG. 17 well demonstrates these twodistinct pore-filling steps. These separated pore-filling steps were notobserved in the case of UTL. The physicochemical data related to thechannel and pore systems of IM-12 and CIT-13 were summarized in Table 8.

The novel germanosilicate CIT-13 showed a ²⁹Si NMR spectrum largelysimilar to that of IM-12, and no silanol group was detected. In the ²⁹SiMAS NMR spectra, both of the two materials showed multiple peakssignificantly overlapping one another in the region from −110 to −120ppm, indicating that both as-calcined CIT-13 and IM-12 in this work areexclusively composed of Q4 Si and having no silanol group (see FIG.16(B)). IM-12 apparently showed more peaks than CIT-13 in this Q4Si-region indicating that the framework UTL has morecrystallographically different T-atoms than CIT-13. This is consistentwith the fact that the framework UTL has 12 T-atom sites in a unit cell,whereas CIT-13 has only 7. Also, there were shoulder-signals in thedownfield region from −105 to −110 ppm that can be assigned as either Siatoms residing in the D4R units 6 or nSi-(4-n)Ge silicon atoms butmaking unanimous peak assignments was limited in this case.

Example 8

Use of Ammonium Fluoride (NH₄F) instead of HF. CIT-13 was also preparedusing NH₄F avoiding the use of harmful and dangerous HF. This protocolinspired the fact that NH₄F can do the same Brønsted acid-baseneutralization reaction, as does HF, in the course of the gelpreparation with quaternary amine hydroxides (OSDA+OH—) which are strongbases. A molar equivalent amount of NH₄F salt was used replacing HF.Ammonia was isolated and removed by drying the gel thoroughly using anair flow until the appearance of the gel became very powdery. A 160° C.static oven was used to crystallization. CIT-13 from the classicprotocol from the reference condition was also synthesized and used as acomparison. For both methods, OSDA 2 was used as the structure-directingagent. These CIT-13 samples from these two methods were studied usingXRD, SEM, EDS, TGA and argon adsorption at 87 K. The results weresummarized in FIG. 18. The successful drying step of NH₃ resulted in themixture having the same gel composition to the product from the classicHF-protocol, effectively providing the way to avoid the use ofconcentrated hydrogen fluoride in CIT-13 synthesis.

Consequently, CIT-13 from this NH₄F-protocol was essentially identicalto CIT-13 from the classic HF-protocol, showing no meaningful differencebetween the two in physicochemical properties. This indicates that allof ammonia initially present in the system could be successfullyevaporated by an extensive drying step, leaving pairs of H+ and F—behind. In powder XRD profiles, (FIG. 18(A)) both samples have shownpure CIT-13 phase with no impurity peak. The SEM images displayed inFIGS. 18(B) and 18(C) also supported the conclusion that the macroscopicmorphologies of CIT-13 crystals were not so different to one another;the twinning within each crystallite was also observed in both samples.The Si/Ge ratios of CIT-13/HF and CIT-13/NH₄F were 5.03±0.48 and5.19±0.15, respectively. The TGA studies also revealed that the weightloss data is very similar: 16.5% for CIT-13/HF and 16.1% forCIT-13/NH₄F. (FIG. 18(D)). More interestingly, according to the argonadsorption isotherms of the two CIT-13s after calcination shown in FIG.18(E), CIT-13 from the NH₄F-protocol also demonstrated thecharacteristic two-step adsorption of extra-large-pore CIT-13 having10MR channels of a high eccentricity shown in FIG. 15. The microporevolumes of CIT-13/NH₄F characterized using the t-plot method and theSF-method were 0.191 cm³/g and 0.215 cm³/g.

As those skilled in the art will appreciate, numerous modifications andvariations of the present invention are possible in light of theseteachings, and all such are contemplated hereby. All references citedherein are incorporated by reference herein, at least for theirteachings in the context presented.

What is claimed:
 1. A process comprising: contacting a chemical streamwith a catalyst comprising a crystalline microporous germanosilicatecomposition; wherein the crystalline microporous germanosilicatecomposition comprises a three-dimensional framework having pores definedby 10- and 14-membered rings and having a ratio of Si:Ge atoms in arange of from 2:1 to 16:1, and further wherein the crystallinemicroporous germanosilicate composition exhibits a powder X-raydiffraction (XRD) pattern exhibiting at least five peaks at 6.45±0.2,7.18±0.2, 12.85±0.2, 20.78±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ;wherein the process is directed to: (a) carbonylating DME with CO at lowtemperatures; (b) reducing NOx with methane: (c) cracking,hydrocracking, or dehydrogenating a hydrocarbon; (d) dewaxing ahydrocarbon feedstock; (e) converting paraffins to aromatics: (f)isomerizing or disproportionating an aromatic feedstock; (g) alkylatingan aromatic hydrocarbon; (h) oligomerizing an alkene; (i) aminating alower alcohol; (j) separating and sorbing a lower alkane from ahydrocarbon feedstock; (k) isomerizing an olefin; (l) producing a highermolecular weight hydrocarbon from lower molecular weight hydrocarbon;(m) reforming a hydrocarbon; (n) converting a lower alcohol or otheroxygenated hydrocarbon to produce an olefin product; (o) epoxidingolefins with hydrogen peroxide; (p) reducing the content of an oxide ofnitrogen contained in a gas stream in the presence of oxygen; (q)separating nitrogen from a nitrogen-containing gas mixture; or (r)converting synthesis gas containing hydrogen and carbon monoxide to ahydrocarbon stream; or (s) reducing the concentration of an organichalide in an initial hydrocarbon product and wherein the contacting isconducted under conditions sufficient to carry out the process of anyone of (a) to (s).
 2. The process of claim 1, wherein the chemicalstream comprises a hydrocarbon feedstock and the process is directed to:(c) cracking, hydrocracking, or dehydrogenating a hydrocarbon; (d)dewaxing the hydrocarbon feedstock; (e) converting paraffins toaromatics: (f) isomerizing or disproportionating an aromatic feedstock;(g) alkylating an aromatic hydrocarbon; (h) oligomerizing an alkene; (j)separating and sorbing a lower alkane from a hydrocarbon feedstock; (k)isomerizing an olefin; (l) producing a higher molecular weighthydrocarbon from lower molecular weight hydrocarbon; (m) reforming ahydrocarbon; or (o) epoxiding an olefin with hydrogen peroxide.
 3. Theprocess of claim 1, wherein the chemical stream comprises a synthesisgas containing hydrogen and carbon monoxide, and the process is directedto converting the synthesis gas containing hydrogen and carbon monoxideto a hydrocarbon stream using a catalyst comprising the crystallinemicroporous germanosilicate composition and a Fischer-Tropsch catalyst.4. The process of claim 1, wherein the chemical stream comprises aninitial hydrocarbon product containing an undesirable level of theorganic halide, and the process comprises contacting at least a portionof the initial hydrocarbon product with a composition comprising thecrystalline microporous germanosilicate composition, under organichalide absorption conditions to reduce the halogen concentration in thehydrocarbon.
 5. The process of claim 1, wherein the crystallinemicroporous germanosilicate composition comprising a three-dimensionalframework having pores defined by 10- and 14-membered rings and having aratio of Si:Ge atoms in a range of from 2:1 to 16:1 exhibits at leastone of: (a) a powder X-ray diffraction (XRD) pattern exhibiting at leastseven of the characteristic peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2,18.26±0.2, 18.36±0.2, 18.63±0.2, 20.78±0.2, 21.55±0.2, 23.36±0.2,24.55±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ; (b) a powder X-raydiffraction (XRD) pattern the same as shown in FIG. 1(B) or FIG. 1(C);or (c) representative unit cell parameters according to: Space groupCmmm a (Å) 27.4374(5) b (Å) 13.8000(2) c (Å) 10.2910(2) V (Å³) 3896.6(1)Z 8 ρ (g/cm³) 2.144(2) λ (Å) 0.776381(1).


6. The process of claim 1, wherein the crystalline microporousgermanosilicate composition exhibits a powder X-ray diffraction (XRD)pattern exhibiting at least seven of the characteristic peaks at6.45±0.2, 7.18±0.2, 12.85±0.2, 18.26±0.2, 18.36±0.2, 18.63±0.2,20.78±0.2, 21.55±0.2, 23.36±0.2, 24.55±0.2, 26.01±0.2, and 26.68±0.2degrees 2-θ.
 7. The process of claim 1, wherein the pore dimensions ofthe 10- and 14-membered rings in the crystalline microporousgermanosilicate composition are 6.2×4.5 Å and 9.1×7.2 Å, respectively.8. The process of claim 1, wherein the ratio of Si:Ge atoms in thecrystalline microporous germanosilicate composition is in a range offrom 2:1 to 8:1.
 9. The process of claim 1, wherein the crystallinemicroporous germanosilicate composition is impregnated with at least onemetal or metal oxide of a transition metal.
 10. The process of claim 9,wherein transition metal or transition metal oxide comprises scandium,yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum,tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel,palladium, platinum, copper, silver, gold, or a mixture thereof.
 11. Theprocess of claim 9, wherein transition metal or transition metal oxidecomprises Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, or a mixturethereof.
 12. The process of claim 1, wherein the chemical streamcontains DME, and the process is directed to (a) carbonylating DME withCO at low temperatures.
 13. The process of claim 1, wherein the chemicalstream contains nitrogen or an oxide thereof, and the process isdirected to (b) reducing NOx with methane: (p) reducing the content ofan oxide of nitrogen contained in a gas stream in the presence ofoxygen; (q) separating nitrogen from a nitrogen-containing gas mixture.14. The process of claim 1, wherein the chemical stream contains a loweralcohol or other oxygenated hydrocarbon and the process is directed to:(i) aminating the lower alcohol; or (n) converting the lower alcohol orother oxygenated hydrocarbon to produce an olefin product.